N-acyl-2-(cyclo)alkypyrrolidines and piperidines useful as fungicides

ABSTRACT

The present invention relates to fungicidal 1-(pyrazolylcarbonyl)piperidines or pyrrolidines, and their thiocarbonyl derivatives, their process of preparation and intermediate compounds for their preparation, their use as fungicides, particularly in the form of fungicidal compositions and methods for the control of phytopathogenic fungi of plants using these compounds or their compositions.

The present invention relates to fungicidal 1-(pyrazolylcarbonyl)piperidines or pyrrolidines, and their thiocarbonyl derivatives, theirprocess of preparation and intermediate compounds for their preparation,their use as fungicides, particularly in the form of fungicidalcompositions and methods for the control of phytopathogenic fungi ofplants using these compounds or their compositions.

In international patent application WO-2009/153191 certain fungicidalproline amides are generically embraced in a broad disclosure ofnumerous compounds of the following formula:

wherein A can represent a substituted pyrazole or a substitutedpyridine, R₁ and R₂ can represent various substituent among which ahydrogen atom or a C₁-C₆-alkyl group, G can represent a bond, an oxygenatom, a sulfur atom, a CH₂ or a (CH₂)₂ moiety, and B can represent a(un)substituted phenyl ring. However, there is no explicit disclosure orsuggestion to select in this document of any such derivative wherein Bcan represent an alkyl group, a cycloalkyl group or a bi- or tricyclylgroup.

In international patent application DE3641343 certain fungicidalheterocyclylcarbonylimidazoles are generically embraced in a broaddisclosure of numerous compounds of the following formula:

wherein Y can represent a hydrogen atom or a C₁-C₄-alkyl group, n can beequal to 5 or 6, m can be equal to 1 to 2, and R can represent varioussubstituent among which a C₁-C₁₀-alkoxy group, aC₁-C₁₀-alkoxy-C₁-C₆-alkyl, a C₁-C₁₀-alkylsulfanyl-C₁-C₅-alkyl group, aC₃-C₆-cycloalkoxy group, a C₃-C₆-cycloalkoxy-C₁-C₆-alkyl, aC₃-C₆-cycloalkylsulfanyl-C₁-C₅-alkyl group, or the like. However, thereis no disclosure or suggestion in this document of any such derivativewherein the imidazole moiety can be replaced by a carbo-linked5-membered heterocyclyl group. Furthermore, there is no explicitdisclosure or suggestion to select in this document of any suchderivative wherein Y can contain a bicyclyl or tricyclyl moiety.

It is always of high interest in the field of agrochemicals to usepesticidal compounds more active than the compounds already known by theman ordinary skilled in the art whereby reduced amounts of compound canbe used whilst retaining equivalent efficacy.

Furthermore, the provision of new pesticidal compounds with a higherefficacy strongly reduces the risk of appearance of resistant strains inthe fungi to be treated.

We have now found a new family of compounds which show enhancedfungicidal activity over the general known family of such compounds.

Accordingly, the present invention provides a1-(pyrazolyl[thio]carbonyl) piperidine or pyrrolidine derivative offormula (I)

wherein

-   -   T represents O or S;    -   n represents 0, 1, 2 or 3;    -   p represents 1 or 2;    -   Q¹ represents a direct bond; O; S; SO; or SO₂; provided that        when n represents 0 then Q¹ represents a direct bond; Z¹ and Z²        independently represent a hydrogen atom; a halogen atom; cyano;        substituted or non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl        having 1 to 5 halogen atoms; substituted or non-substituted        C₁-C₈-alkoxy; substituted or non-substituted        C₁-C₈-alkylsulfanyl; or substituted or non-substituted        C₁-C₈-alkoxycarbonyl; or    -   two substituents Z¹ and Z², together with the carbon atom to        which they are linked can form a 3-, 4-, 5- or 6-membered        saturated carbocycle that can be substituted by up to four        C₁-C₈-alkyl groups;    -   Z³ represents a hydrogen atom; or substituted or non-substituted        C₁-C₈-alkyl;    -   B represents a substituted or non-substituted C₁-C₈-alkyl;        C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms; substituted or        non-substituted C₁-C₈-alkoxy-C₁-C₈-alkyl; substituted or        non-substituted C₁-C₈-alkylsulfanyl-C₁-C₈-alkyl; substituted or        non-substituted C₁-C₈-alkylsulfinyl-C₁-C₈-alkyl; substituted or        non-substituted C₁-C₈-alkylsulfonyl-C₁-C₈-alkyl; substituted or        non-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl        having 1 to 9 halogen atoms; substituted or non-substituted        (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl; substituted or non-substituted        C₄-C₇-cycloalkenyl; C₄-C₇-halogenocycloalkenyl having 1 to 9        halogen atoms; substituted or non-substituted        (C₄-C₇-cycloalkenyl)-C₁-C₈-alkyl; substituted or non-substituted        bicyclo[2.2.1]heptanyl; substituted or non-substituted        bicyclo[2.2.1]hept-2-enyl; substituted or non-substituted        bicyclo[2.2.2]octanyl; substituted or non-substituted        bicyclo[2.2.2]oct-2-enyl; substituted or non-substituted        adamantyl; provided that when n represents 0 and Q¹ represents a        direct bond then B is not methyl or ethyl;    -   R¹ and R³ independently represent a halogen atom; nitro; cyano;        hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl; substituted        or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl substituted        or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; substituted or        non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9        halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;        C₂-C₈-halogenoalkenyl having 1 to 9 halogen atoms; substituted        or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1        to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;        C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms; substituted or        non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl        having 1 to 9 halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9        halogen atoms substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₂-C₈-alkenyloxy; substituted or        non-substituted C₃-C₈-alkynyloxy; substituted or non-substituted        C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9 halogen        atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;        substituted or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted        or non-substituted di-C₁-C₈-alkylcarbamoyl; phenoxy        phenylsulfanyl; phenylamino; benzyloxy; benzylsulfanyl; or        benzylamino;    -   R² represents a hydrogen atom; halogen atom; nitro; cyano;        hydroxy; amino; sulfanyl pentafluoro-λ⁶-sulfanyl; substituted or        non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl substituted or        non-substituted (benzyloxyimino)-C₁-C₈-alkyl; substituted or        non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9        halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;        C₂-C₈-halogenoalkenyl having 1 to 9 halogen atoms; substituted        or non-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1        to 9 halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;        C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms; substituted or        non-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl        having 1 to 9 halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9        halogen atoms; substituted or non-substituted        C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 9        halogen atoms; substituted or non-substituted C₁-C₈-alkylamino;        substituted or non-substituted di-C₁-C₈-alkylamino; substituted        or non-substituted C₂-C₈-alkenyloxy; substituted or        non-substituted C₃-C₈-alkynyloxy; substituted or non-substituted        C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9 halogen        atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;        substituted or non-substituted C₁-C₈-alkylcarbonyl;        C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkoxycarbonyl;        C₁-C₈-halogenoalkoxycarbonyl having 1 to 9 halogen atoms;        substituted or non-substituted C₁-C₈-alkylcarbamoyl; substituted        or non-substituted di-C₁-C₈-alkylcarbamoyl; phenoxy        phenylsulfanyl; phenylamino; benzyloxy; benzylsulfanyl; or        benzylamino;        as well as its salts, N-oxides, metal complexes, metalloid        complexes and optically active isomers, provided that the        following compounds are excluded:

-   [2-(chloromethyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   [2-(chloromethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   [2-(3-chloropropyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   (3-tert-butyl-1-methyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone

-   (3-tert-butyl-1-isopropyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone

-   (1,3-dimethyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone

-   [2-(2-hydroxyethyl)piperidin-1-yl](1-isopropyl-3-methyl-1H-pyrazol-4-yl)methanone

-   {1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]pyrrolidin-2-yl}acetic    acid

-   [2-(hydroxymethyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   {2-[(methylamino)methyl]piperidin-1-yl}(1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   [2-(2-chloroethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   [(2S)-2-(chloromethyl)pyrrolidin-1-yl][3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]methanone

-   [3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl][(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]methanone

-   [2-(methoxymethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   [2-(2-hydroxyethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone

-   {1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]piperidin-2-yl}acetic    acid

-   methyl    {1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]piperidin-2-yl}acetate

-   [2-(hydroxymethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone.

Unless indicated otherwise, a group or a substituent that is substitutedaccording to the invention can be substituted by one or more of thefollowing groups or atoms: a halogen atom; nitro; hydroxyl; cyano;isonitrile; sulfanyl; a pentafluoro-λ⁶-sulfanyl group; formyl;formyloxy; formylamino; carbamoyl; N-hydroxycarbamoyl; carbamate;(hydroxyimino)-C₁-C₆-alkyl; C₁-C₈-alkyl; a tri(C₁-C₈-alkyl)silyl;C₃-C₈-cycloalkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogen atoms; aC₃-C₈-halogenocycloalkyl having 1 to 5 halogen atoms; C₂-C₈-alkenyl;C₂-C₈-alkynyl; C₂-C₈-alkenyloxy; C₂-C₈-alkynyloxy; C₁-C₈-alkylamino;di-C₁-C₈-alkylamino; C₁-C₈-alkoxy; C₁-C₈-halogenoalkoxy having 1 to 5halogen atoms; C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having 1to 5 halogen atoms; C₂-C₈-alkenyloxy; C₂-C₈-halogenoalkenyloxy having 1to 5 halogen atoms; C₃-C₈-alkynyloxy; C₃-C₈-halogenoalkynyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonyl; C₁-C₈-halogenoalkylcarbonylhaving 1 to 5 halogen atoms; C₁-C₈-alkylcarbamoyl;di-C₁-C₈-alkylcarbamoyl; N—C₁-C₈-alkyloxycarbamoyl;C₁-C₈-alkoxycarbamoyl; N—C₁-C₈-alkyl-C₁-C₈-alkoxycarbamoyl;C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonyl having 1 to 5 halogenatoms; C₁-C₈-alkylcarbonyloxy; C₁-C₈-halogenoalkylcarbonyloxy having 1to 5 halogen atoms; C₁-C₈-alkylcarbonylamino;C₁-C₈-halogenoalkylcarbonylamino having 1 to 5 halogen atoms;C₁-C₈-alkylaminocarbonyloxy; di-C₁-C₈-alkylaminocarbonyloxy;C₁-C₈-alkyloxycarbonyloxy; C₁-C₈-alkylsulfanyl;C₁-C₈-halogenoalkylsulfanyl having 1 to 5 halogen atoms;C₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 5 halogenatoms; C₁-C₈-alkylsulfonyl; C₁-C₈-halogenoalkylsulfonyl having 1 to 5halogen atoms; C₁-C₈-alkylaminosulfamoyl; di-C₁-C₈-alkylaminosulfamoyl;(C₁-C₆-alkoxyimino)-C₁-C₆-alkyl; (C₁-C₆-alkenyloxyimino)-C₁-C₆-alkyl;(C₁-C₆-alkynyloxyimino)-C₁-C₆-alkyl; 2-oxopyrrolidin-1-yl;(benzyloxyimino)-C₁-C₆-alkyl; C₁-C₈-alkoxyalkyl;C₁-C₈-halogenoalkoxyalkyl having 1 to 5 halogen atoms; benzyloxy;benzylsulfanyl; benzylamino; aryloxy; arylsulfanyl or arylamino.

For the compounds according to the invention, the following genericterms are generally used with the following meanings:

-   -   halogen means fluorine, bromine, chlorine or iodine.    -   carboxy means —C(═O)OH;    -   carbonyl means —C(═O)—;    -   carbamoyl means —C(═O)NH₂;    -   N-hydroxycarbamoyl means —C(═O)NHOH;    -   SO represents a sulfoxide group;    -   SO₂ represents a sulfone group;    -   methylene means the diradical —CH₂—;    -   an alkyl group, an alkenyl group and an alkynyl group as well as        moieties containing these terms, can be linear or branched;    -   heteroatom means sulfur, nitrogen or oxygen.    -   halogenated groups, notably haloalkyl, haloalkoxy and cycloalkyl        groups, can comprise up to nine identical or different halogen        atoms;    -   the term “aryl” means phenyl or naphthyl;    -   in the case of an amino group or the amino moiety of any other        amino-comprising group, substituted by two substituent that can        be the same or different, the two substituent together with the        nitrogen atom to which they are linked can form a heterocyclyl        group, preferably a 5- to 7-membered heterocyclyl group, that        can be substituted or that can include other hetero atoms, for        example a morpholino group or piperidinyl group.    -   Where a compound of the invention can be present in tautomeric        form, such a compound is understood hereinabove and hereinbelow        also to include, where applicable, corresponding tautomeric        forms, even when these are not specifically mentioned in each        case.

Any of the compounds of the present invention can exist in one or moreoptical or chiral isomer forms depending on the number of asymmetriccentres in the compound. The invention thus relates equally to all theoptical isomers and to their racemic or scalemic mixtures (the term“scalemic” denotes a mixture of enantiomers in different proportions)and to the mixtures of all the possible stereoisomers, in allproportions. The diastereoisomers and/or the optical isomers can beseparated according to the methods which are known per se by the manordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the number of double bonds inthe compound. The invention thus relates equally to all geometricisomers and to all possible mixtures, in all proportions. The geometricisomers can be separated according to general methods, which are knownper se by the man ordinary skilled in the art.

Any of the compounds of the present invention can also exist in one ormore geometric isomer forms depending on the relative position (syn/antior cis/trans or endo/exo) of the substituents of any chain or ring. Theinvention thus relates equally to all syn/anti (or cis/trans orendo/exo) isomers and to all possible syn/anti (or cis/trans orendo/exo) mixtures, in all proportions. The syn/anti (or cis/trans orendo/exo) isomers can be separated according to general methods, whichare known per se by the man ordinary skilled in the art.

Preferred compounds according to the invention are compounds of formula(I) wherein R¹ represents a substituted or non-substituted C₁-C₅-alkyl,C₁-C₅-halogenoalkyl comprising up to 9 halogen atoms that can be thesame or different, substituted or non-substituted C₁-C₅-alkoxy; R²represents a hydrogen atom, or a halogen atom; and R³ represents asubstituted or non-substituted C₁-C₅-alkyl.

More preferred compounds according to the invention are compounds offormula (I) wherein R¹ represents C₁-C₅-alkyl, C₁-C₅-halogenoalkylcomprising up to 3 halogen atoms that can be the same or different; R²represents a hydrogen atom, a chlorine atom, or a fluorine atom; and R³represents a methyl.

Even more preferred compounds according to the invention are compoundsof formula (I) wherein R¹ represents difluoromethyl; R² represents achlorine atom, or a fluorine atom; and R³ represents a methyl.

Other preferred compounds according to the invention are compounds offormula (I) wherein T represents O.

Other preferred compounds according to the invention are compounds offormula (I) wherein p represents 1.

Other preferred compounds according to the invention are compounds offormula (I) wherein p represents 2.

Other preferred compounds according to the invention are compounds offormula (I) wherein n represents 0 or 1.

Other preferred compounds according to the invention are compounds offormula (I) wherein Q¹ represents a direct bond or an oxygen atom.

Other more preferred compounds according to the invention are compoundsof formula (I) wherein Q¹ represents a direct bond.

Other preferred compounds according to the invention are compounds offormula (I) wherein B represents a substituted or non-substitutedC₁-C₈-alkyl, substituted or non-substituted C₃-C₇-cycloalkyl,substituted or non-substituted bicyclo[2.2.1]hept-2-yl, substituted ornon-substituted bicyclo[2.2.2]oct-2-yl or substituted or non-substitutedadamantan-1-yl.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z¹ and Z² independently represents a hydrogen atom,a halogen, substituted or non-substituted C₁-C₈-alkyl or substituted ornon-substituted C₁-C₈-alkoxy.

Other preferred compounds according to the invention are compounds offormula (I) wherein Z³ represents a hydrogen atom.

The above mentioned preferences with regard to the substituents of thecompounds according to the invention can be combined in various manners.These combinations of preferred features thus provide sub-classes ofcompounds according to the invention. Examples of such sub-classes ofpreferred compounds according to the invention are:

preferred features of R¹ with preferred features of R², R³, T, p, n, Z¹to Z³, Q¹, and B;

preferred features of R² with preferred features of R¹, R³, T, p, n, Z¹to Z³, Q¹, and B;

preferred features of R³ with preferred features of R¹, R², T, p, n, Z¹to Z³, Q¹, and B;

preferred features of T with preferred features of R¹ to R³, p, n, Z¹ toZ³, Q¹, and B;

preferred features of p with preferred features of R¹ to R³, T, n, Z¹ toZ³, Q¹, and B;

preferred features of n with preferred features of R¹ to R³, T, p, Z¹ toZ³, Q¹, and B;

preferred features of Z¹ with preferred features of R¹ to R³, T, p, n,Z² to Z³, Q¹, and B;

preferred features of Z² with preferred features of R¹ to R³, T, p, n,Z¹, Z³, Q¹, and B;

preferred features of Z³ with preferred features of R¹ to R³, T, p, n,Z¹ to Z², Q¹, and B;

preferred features of Q¹ with preferred features of R¹ to R³, T, p, n,Z¹ to Z³ and B;

preferred features of B with preferred features of R¹ to R³, T, p, n, Z¹to Z³ and Q¹.

In these combinations of preferred features of the substituents of thecompounds according to the invention, the said preferred features canalso be selected among the more preferred features of each of R¹ to R³,T, p, n, Z¹ to Z³, Q¹, and B so as to form most preferred subclasses ofcompounds according to the invention.

The present invention also relates to a process for the preparation ofthe compound of formula (I). Thus, according to a further aspect of thepresent invention there is provided a process P1 for the preparation ofa compound of formula (I) as herein-defined and wherein T represents Oand that comprises reaction of a piperidine or pyrrolidine of formula(II) or one of its salts:

wherein Z¹, Z², Z³, p, n, Q¹ and B are as herein-defined; with acarboxylic acid derivative of formula (III):

wherein R¹, R², R³ is as herein-defined and U¹ represents a leavinggroup selected in the list consisting of a halogen atom, a hydroxylgroup, —OR^(a), —OC(═O)R^(a), R^(a) being a substituted ornon-substituted C₁-C₆-alkyl, a substituted or non-substitutedC₁-C₆-haloalkyl, a benzyl, 4-methoxybenzyl or pentafluorophenyl group,or a group of formula O—C(═O)-(1-R³-3-R¹-5-R²-pyrazol-4-yl); in thepresence of a catalyst and in the presence of a condensing agent in caseU¹ represents a hydroxyl group, and in the presence of an acid binder incase U¹ represents a halogen atom.

Piperidines of formula (II) can be prepared by deprotonation ofN-(diethoxymethyl)piperidin-2-one and condensation of the anion with a1-(cyclo)alkylcarboxylic ester followed a rearrangement with aqueous HCland further reduction of the obtained cylic imine (Tetrahedron (2011),67(1), 69-74).

Pyrrolidines of formula (II) can be prepared by deprotonation ofN-vinylpyrrolidin-2-one and condensation of the anion with a1-(cyclo)alkylcarboxylic ester followed a rearrangement with aqueous HCland further reduction of the obtained cylic imine (Tetrahedron (2011),67(1), 69-74).

Carboxylic acid derivatives of formula (III) can be prepared by knownprocesses.

In case U¹ represents a hydroxy group, process P1 according to thepresent invention is conducted in the presence of condensing agent.Suitable condensing agent may be selected in the non limited listconsisting of acid halide former, such as phosgene, phosphoroustribromide, phosphorous trichloride, phosphorous pentachloride,phosphorous trichloride oxide or thionyl chloride; anhydride former,such as ethyl chloroformate, methyl chloroformate, isopropylchloroformate, isobutyl chloroformate or methanesulfonyl chloride;carbodiimides, such as N,N′-dicyclohexylcarbodiimide (DCC) or othercustomary condensing agents, such as phosphorous pentoxide,polyphosphoric acid, N,N′-carbonyl-diimidazole,2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ),triphenylphosphine/tetrachloro-methane,4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloridehydrate, bromo-tripyrrolidinophosphoniumhexafluorophosphate orpropanephosphonic anhydride (T3P).

Process P1 according to the present invention can be conducted in thepresence of a catalyst. Suitable catalyst may be selected in the listconsisting of N,N-dimethylpyridin-4-amine, 1-hydroxy-benzotriazole orN,N-dimethylformamide.

In case U¹ represents a halogen atom, process P1 according to thepresent invention is conducted in the presence of an acid binder.Suitable acid binders for carrying out process P1 according to theinvention are in each case all inorganic and organic bases that arecustomary for such reactions. Preference is given to using alkalineearth metal, alkali metal hydride, alkali metal hydroxides or alkalimetal alkoxides, such as sodium hydroxide, sodium hydride, calciumhydroxide, potassium hydroxide, potassium tert-butoxide or otherammonium hydroxide, alkali metal carbonates, such as caesium carbonate,sodium carbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate, alkali metal or alkaline earth metal acetates, such assodium acetate, potassium acetate, calcium acetate and also tertiaryamines, such as trimethylamine, triethylamine, diisopropylethylamine,tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine,N,N-dimethylpyridin-4-amine, diazabicyclooctane (DABCO),diazabicyclo-nonene (DBN) or diazabicycloundecene (DBU).

It is also possible to work in the absence of an additional condensingagent or to employ an excess of the piperidine or pyrrolidine or formula(II), so that it simultaneously acts as acid binder agent.

Suitable solvents for carrying out process P1 according to the inventioncan be customary inert organic solvents. Preference is given to usingoptionally halogenated aliphatic, alicyclic or aromatic hydrocarbons,such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane; ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole;nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile; amides, such as N,N-dimethylformamide,N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone, orhexamethylphosphoric triamide; alcohols such as methanol, ethanol,propanol, iso-propanol; esters, such as methyl acetate or ethyl acetate,sulfoxides, such as dimethyl sulfoxide, or sulfones, such as sulfolane.

When carrying out process P1 according to the invention, the piperidineor pyrrolidine of formula (II) can be employed as its salt, such aschlorhydrate or any other convenient salt.

When carrying out process P1 according to the invention, 1 mole or anexcess of the piperidine or pyrrolidine of formula (II) and from 1 to 3moles of the acid binder can be employed per mole of the reagent offormula (III).

It is also possible to employ the reaction components in other ratios.Work-up is carried out by known methods.

According to a further aspect according to the invention, there isprovided a process P2 for the preparation of a compound of formula (I)wherein T represents S, starting from a compound of formula (I) whereinT represents O and illustrated according to the following reactionscheme:

wherein R¹, R², R³, Z¹, Z², Z³, p, n, Q¹ and B are as herein-defined, inthe optionally presence of a catalytic or stoichiometric or excessamount, quantity of a base such as an inorganic and organic base.Preference is given to using alkali metal carbonates, such as sodiumcarbonate, potassium carbonate, potassium bicarbonate, sodiumbicarbonate; heterocyclic aromatic bases, such as pyridine, picoline,lutidine, collidine; and also tertiary amines, such as trimethylamine,triethylamine, tributylamine, N,N-dimethylaniline,N,N-dimethylaminopyridine or N-methyl-piperidine.

Process P2 according to the invention is performed in the presence of athionating agent.

Starting amide derivatives of formula (I) can be prepared according toprocesses P1.

Suitable thionating agents for carrying out process P2 according to theinvention can be sulfur (S), sulfhydric acid (H₂S), sodium sulfide(Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃),bis(diethylaluminium) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S),phosphorous pentasulfide (P₂S₅), Lawesson's reagent(2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide) ora polymer-supported thionating reagent such as described in Journal ofthe Chemical Society, Perkin 1 (2001), 358, in the optionally presenceof a catalytic or stoichiometric or excess amount, quantity of a basesuch as an inorganic and organic base. Preference is given to usingalkali metal carbonates, such as sodium carbonate, potassium carbonate,potassium bicarbonate, sodium bicarbonate; heterocyclic aromatic bases,such as pyridine, picoline, lutidine, collidine; and also tertiaryamines, such as trimethylamine, triethylamine, tributylamine,N,N-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.

Suitable solvents for carrying out process P2 according to the inventioncan be customary inert organic solvents. Preference is given to usingoptionally halogenated aliphatic, alicyclic or aromatic hydrocarbons,such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene,dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride,dichlorethane or trichlorethane, ethers, such as diethyl ether,diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane,tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane, nitriles,such as acetonitrile, propionitrile, n- or i-butyronitrile orbenzonitrile, sulfurous solvents, such as sulfolane or carbon disulfide.

When carrying out process P2 according to the invention, 1 mole or anexcess of the sulfur equivalent of the thionating agent and from 1 to 3moles of the base can be employed per mole of the amide reactant (I).

It is also possible to employ the reaction components in other ratios.Work-up is carried out by known methods.

Processes P1 and P2 according to the invention are generally carried outunder atmospheric pressure. It is also possible to operate underelevated or reduced pressure.

When carrying out processes P1 and P2 according to the invention, thereaction temperatures can be varied within a relatively wide range. Ingeneral, these processes are carried out at temperatures from 0° C. to200° C., preferably from 10° C. to 150° C. A way to control thetemperature for the processes according to the invention is to usemicro-wave technology.

In general, the reaction mixture is concentrated under reduced pressure.The residue that remains can be freed by known methods, such aschromatography or crystallization, from any impurities that can still bepresent.

Work-up is carried out by customary methods. Generally, the reactionmixture is treated with water and the organic phase is separated offand, after drying, concentrated under reduced pressure. If appropriate,the remaining residue can, be freed by customary methods, such aschromatography, crystallization or distillation, from any impuritiesthat may still be present.

The compound according to the present invention can be preparedaccording to the general processes of preparation described above. Itwill nevertheless be understood that, on the basis of his generalknowledge and of available publications, the skilled worker will be ableto adapt this method according to the specifics of each of thecompounds, which it is desired to synthesize.

In a further aspect, the present invention also relates to a fungicidecomposition comprising an effective and non-phytotoxic amount of anactive compound of formula (I).

The expression “effective and non-phytotoxic amount” means an amount ofcomposition according to the invention that is sufficient to control ordestroy the fungi present or liable to appear on the crops and that doesnot entail any appreciable symptom of phytotoxicity for the said crops.Such an amount can vary within a wide range depending on the fungus tobe controlled, the type of crop, the climatic conditions and thecompounds included in the fungicide composition according to theinvention. This amount can be determined by systematic field trials thatare within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicidecomposition comprising, as an active ingredient, an effective amount ofa compound of formula (I) as herein defined and an agriculturallyacceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural orsynthetic, organic or inorganic compound with that the active compoundof formula (I) is combined or associated to make it easier to apply,notably to the parts of the plant. This support is thus generally inertand should be agriculturally acceptable. The support can be a solid or aliquid. Examples of suitable supports include clays, natural orsynthetic silicates, silica, resins, waxes, solid fertilisers, water,alcohols, in particular butanol, organic solvents, mineral and plantoils and derivatives thereof. Mixtures of such supports can also beused.

The composition according to the invention can also comprise additionalcomponents. In particular, the composition can further comprise asurfactant. The surfactant can be an emulsifier, a dispersing agent or awetting agent of ionic or non-ionic type or a mixture of suchsurfactants. Mention can be made, for example, of polyacrylic acidsalts, lignosulfonic acid salts, phenolsulfonic or naphthalenesulfonicacid salts, polycondensates of ethylene oxide with fatty alcohols orwith fatty acids or with fatty amines, substituted phenols (inparticular alkylphenols or arylphenols), salts of sulfosuccinic acidesters, taurine derivatives (in particular alkyl taurates), phosphoricesters of polyoxyethylated alcohols or phenols, fatty acid esters ofpolyols and derivatives of the above compounds containing sulfate,sulfonate and phosphate functions. The presence of at least onesurfactant is generally essential when the active compound and/or theinert support are water-insoluble and when the vector agent for theapplication is water. Preferably, surfactant content can be comprisedfrom 5% to 40% by weight of the composition.

Optionally, additional components can also be included, e.g. protectivecolloids, adhesives, thickeners, thixotropic agents, penetration agents,stabilisers, sequestering agents. More generally, the active compoundscan be combined with any solid or liquid additive, that complies withthe usual formulation techniques.

In general, the composition according to the invention can contain from0.05 to 99% by weight of active compound, preferably 10 to 70% byweight.

Compositions according to the invention can be used in various forms andformulations such as aerosol dispenser, capsule suspension, cold foggingconcentrate, dustable powder, emulsifiable concentrate, emulsion oil inwater, emulsion water in oil, encapsulated granule, fine granule,flowable concentrate for seed treatment, gas (under pressure), gasgenerating product, granule, hot fogging concentrate, macrogranule,microgranule, oil dispersible powder, oil miscible flowable concentrate,oil miscible liquid, paste, plant rodlet, powder for dry seed treatment,seed coated with a pesticide, soluble concentrate, soluble powder,solution for seed treatment, suspension concentrate (flowableconcentrate), ultra low volume (ULV) liquid, ultra low volume (ULV)suspension, water dispersible granules or tablets, water dispersiblepowder for slurry treatment, water soluble granules or tablets, watersoluble powder for seed treatment and wettable powder. Thesecompositions include not only compositions that are ready to be appliedto the plant or seed to be treated by means of a suitable device, suchas a spraying or dusting device, but also concentrated commercialcompositions that must be diluted before application to the crop.

The formulations can be prepared in a manner known per se, for exampleby mixing the active ingredients with at least one customary extender,solvent or diluent, adjuvant, emulsifier, dispersant, and/or binder orfixative, wetting agent, water repellent, if appropriate desiccants andUV stabilizers and, if appropriate, dyes and pigments, antifoams,preservatives, inorganic and organic thickeners, adhesives, gibberellinsand also further processing auxiliaries and also water. Depending on theformulation type to be prepared further processing steps are necessary,e.g. wet grinding, dry grinding and granulation.

The inventive active ingredients may be present as such or in their(commercial) formulations and in the use forms prepared from theseformulations as a mixture with other (known) active ingredients, such asinsecticides, attractants, sterilants, bactericides, acaricides,nematicides, fungicides, growth regulators, herbicides, fertilizers,safeners and/or semiochemicals.

The compounds of formula (I) and the fungicide composition according tothe invention can be used to curatively or preventively control thephytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provideda method for curatively or preventively controlling the phytopathogenicfungi of plants or crops characterised in that a compound of formula (I)or a fungicide composition according to the invention is applied to theseed, the plant or to the fruit of the plant or to the soil wherein theplant is growing or wherein it is desired to grow.

The method of treatment according to the invention can also be useful totreat propagation material such as tubers or rhizomes, but also seeds,seedlings or seedlings pricking out and plants or plants pricking out.This method of treatment can also be useful to treat roots. The methodof treatment according to the invention can also be useful to treat theoverground parts of the plant such as trunks, stems or stalks, leaves,flowers and fruit of the concerned plant.

According to the invention all plants and plant parts can be treated. Byplants is meant all plants and plant populations such as desirable andundesirable wild plants, cultivars and plant varieties (whether or notprotectable by plant variety or plant breeder's rights). Cultivars andplant varieties can be plants obtained by conventional propagation andbreeding methods which can be assisted or supplemented by one or morebiotechnological methods such as by use of double haploids, protoplastfusion, random and directed mutagenesis, molecular or genetic markers orby bioengineering and genetic engineering methods. By plant parts ismeant all above ground and below ground parts and organs of plants suchas shoot, leaf, blossom and root, whereby for example leaves, needles,stems, branches, blossoms, fruiting bodies, fruits and seed as well asroots, corms and rhizomes are listed. Crops and vegetative andgenerative propagating material, for example cuttings, corms, rhizomes,runners and seeds also belong to plant parts.

Among the plants that can be protected by the method according to theinvention, mention may be made of major field crops like corn, soybean,cotton, Brassica oilseeds such as Brassica napus (e.g. canola), Brassicarapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat,sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vineand various fruits and vegetables of various botanical taxa such asRosaceae sp. (for instance pip fruit such as apples and pears, but alsostone fruit such as apricots, cherries, almonds and peaches, berryfruits such as strawberries), Ribesioidae sp., Juglandaceae sp.,Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceaesp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance bananatrees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp.,Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges andgrapefruit); Solanaceae sp. (for instance tomatoes, potatoes, peppers,eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce,artichoke and chicory—including root chicory, endive or common chicory),Umbelliferae sp. (for instance carrot, parsley, celery and celeriac),Cucurbitaceae sp. (for instance cucumber—including pickling cucumber,squash, watermelon, gourds and melons), Alliaceae sp. (for instanceonions and leek), Cruciferae sp. (for instance white cabbage, redcabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi,radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (forinstance peanuts, peas and beans beans—such as climbing beans and broadbeans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach,beetroots), Malvaceae (for instance okra), Asparagaceae (for instanceasparagus); horticultural and forest crops; ornamental plants; as wellas genetically modified homologues of these crops.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants ofwhich a heterologous gene has been stably integrated into genome. Theexpression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for example,antisense technology, cosuppression technology or RNAinterference—RNAi—technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active compounds and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf color, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active compound combinations accordingto the invention may also have a strengthening effect in plants.Accordingly, they are also suitable for mobilizing the defense system ofthe plant against attack by unwanted microorganisms. This may, ifappropriate, be one of the reasons of the enhanced activity of thecombinations according to the invention, for example against fungi.Plant-strengthening (resistance-inducing) substances are to beunderstood as meaning, in the present context, those substances orcombinations of substances which are capable of stimulating the defensesystem of plants in such a way that, when subsequently inoculated withunwanted microorganisms, the treated plants display a substantial degreeof resistance to these microorganisms. In the present case, unwantedmicroorganisms are to be understood as meaning phytopathogenic fungi,bacteria and viruses. Thus, the substances according to the inventioncan be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active compounds.

Plants and plant cultivars which are preferably to be treated accordingto the invention include all plants which have genetic material whichimpart particularly advantageous, useful traits to these plants (whetherobtained by breeding and/or biotechnological means).

Plants and plant cultivars which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants show a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Examples of nematode resistant plants are described in e.g. U.S. patentapplication Ser. Nos. 11/765,491, 11/765,494, 10/926,819, 10/782,020,12/032,479, 10/783,417, 10/782,096, 11/657,964, 12/192,904, 11/396,808,12/166,253, 12/166,239, 12/166,124, 12/166,209, 11/762,886, 12/364,335,11/763,947, 12/252,453, 12/209,354, 12/491,396 or 12/497,221.

Plants and plant cultivars which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, flooding,increased soil salinity, increased mineral exposure, ozone exposure,high light exposure, limited availability of nitrogen nutrients, limitedavailability of phosphorus nutrients, shade avoidance.

Plants and plant cultivars which may also be treated according to theinvention, are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including but not limited to, early flowering, floweringcontrol for hybrid seed production, seedling vigor, plant size,internode number and distance, root growth, seed size, fruit size, podsize, pod or ear number, seed number per pod or ear, seed mass, enhancedseed filling, reduced seed dispersal, reduced pod dehiscence and lodgingresistance. Further yield traits include seed composition, such ascarbohydrate content, protein content, oil content and composition,nutritional value, reduction in anti-nutritional compounds, improvedprocessability and better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristic of heterosis or hybrid vigorwhich results in generally higher yield, vigor, health and resistancetowards biotic and abiotic stresses). Such plants are typically made bycrossing an inbred male-sterile parent line (the female parent) withanother inbred male-fertile parent line (the male parent). Hybrid seedis typically harvested from the male sterile plants and sold to growers.Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling, i.e. the mechanical removal of the male reproductive organs(or males flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plantsit is typically useful to ensure that male fertility in the hybridplants is fully restored. This can be accomplished by ensuring that themale parents have appropriate fertility restorer genes which are capableof restoring the male fertility in hybrid plants that contain thegenetic determinants responsible for male-sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species (WO 92/05251, WO 95/09910, WO 98/27806, WO05/002324, WO 06/021972 and U.S. Pat. No. 6,229,072). However, geneticdeterminants for male sterility can also be located in the nucleargenome. Male sterile plants can also be obtained by plant biotechnologymethods such as genetic engineering. A particularly useful means ofobtaining male-sterile plants is described in WO 89/10396 in which, forexample, a ribonuclease such as barnase is selectively expressed in thetapetum cells in the stamens. Fertility can then be restored byexpression in the tapetum cells of a ribonuclease inhibitor such asbarstar (e.g. WO 91/02069).

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-resistant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.Plants can be made tolerant to glyphosate through different means. Forexample, glyphosate-tolerant plants can be obtained by transforming theplant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphatesynthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutantCT7) of the bacterium Salmonella typhimurium (Comai et al., 1983,Science 221, 370-371), the CP4 gene of the bacterium Agrobacterium sp.(Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genesencoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481), aTomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or anEleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS asdescribed in for example EP 0837944, WO 00/66746, WO 00/66747 orWO02/26995. Glyphosate-tolerant plants can also be obtained byexpressing a gene that encodes a glyphosate oxido-reductase enzyme asdescribed in U.S. Pat. Nos. 5,776,760 and 5,463,175. Glyphosate-tolerantplants can also be obtained by expressing a gene that encodes aglyphosate acetyl transferase enzyme as described in for example WO02/36782, WO 03/092360, WO 05/012515 and WO 07/024782.Glyphosate-tolerant plants can also be obtained by selecting plantscontaining naturally-occurring mutations of the above-mentioned genes,as described in for example WO 01/024615 or WO 03/013226. Plantsexpressing EPSPS genes that confer glyphosate tolerance are described ine.g. U.S. patent application Ser. Nos. 11/517,991, 10/739,610,12/139,408, 12/352,532, 11/312,866, 11/315,678, 12/421,292, 11/400,598,11/651,752, 11/681,285, 11/605,824, 12/468,205, 11/760,570, 11/762,526,11/769,327, 11/769,255, 11/943801 or 12/362,774. Plants comprising othergenes that confer glyphosate tolerance, such as decarboxylase genes, aredescribed in e.g. U.S. patent application Ser. Nos. 11/588,811,11/185,342, 12/364,724, 11/185,560 or 12/423,926.

Other herbicide resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition, e.g. described in U.S.patent application Ser. No. 11/760,602. One such efficient detoxifyingenzyme is an enzyme encoding a phosphinothricin acetyltransferase (suchas the bar or pat protein from Streptomyces species). Plants expressingan exogenous phosphinothricin acetyltransferase are for exampledescribed in U.S. Pat. Nos. 5,561,236; 5,648,477; 5,646,024; 5,273,894;5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenylpyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD-inhibitors can be transformedwith a gene encoding a naturally-occurring resistant HPPD enzyme, or agene encoding a mutated or chimeric HPPD enzyme as described in WO96/38567, WO 99/24585, WO 99/24586, WO 2009/144079, WO 2002/046387, orU.S. Pat. No. 6,768,044. Tolerance to HPPD-inhibitors can also beobtained by transforming plants with genes encoding certain enzymesenabling the formation of homogentisate despite the inhibition of thenative HPPD enzyme by the HPPD-inhibitor. Such plants and genes aredescribed in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPDinhibitors can also be improved by transforming plants with a geneencoding an enzyme having prephenate deshydrogenase (PDH) activity inaddition to a gene encoding an HPPD-tolerant enzyme, as described in WO2004/024928. Further, plants can be made more tolerant to HPPD-inhibitorherbicides by adding into their genome a gene encoding an enzyme capableof metabolizing or degrading HPPD inhibitors, such as the CYP450 enzymesshown in WO 2007/103567 and WO 2008/150473.

Still further herbicide resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitorsinclude, for example, sulfonylurea, imidazolinone, triazolopyrimidines,pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides, as described for examplein Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S.Pat. Nos. 5,605,011, 5,378,824, 5,141,870, and 5,013,659. The productionof sulfonylurea-tolerant plants and imidazolinone-tolerant plants isdescribed in U.S. Pat. Nos. 5,605,011; 5,013,659; 5,141,870; 5,767,361;5,731,180; 5,304,732; 4,761,373; 5,331,107; 5,928,937; and 5,378,824;and international publication WO 96/33270. Other imidazolinone-tolerantplants are also described in for example WO 2004/040012, WO 2004/106529,WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO2006/024351, and WO 2006/060634. Further sulfonylurea- andimidazolinone-tolerant plants are also described in for example WO07/024782 and U.S. Patent Application No. 61/288,958.

Other plants tolerant to imidazolinone and/or sulfonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding as described for examplefor soybeans in U.S. Pat. No. 5,084,082, for rice in WO 97/41218, forsugar beet in U.S. Pat. No. 5,773,702 and WO 99/057965, for lettuce inU.S. Pat. No. 5,198,599, or for sunflower in WO 01/065922.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

-   -   1) an insecticidal crystal protein from Bacillus thuringiensis        or an insecticidal portion thereof, such as the insecticidal        crystal proteins listed by Crickmore et al. (1998, Microbiology        and Molecular Biology Reviews, 62: 807-813), updated by        Crickmore et al. (2005) at the Bacillus thuringiensis toxin        nomenclature, online at:        http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or        insecticidal portions thereof, e.g., proteins of the Cry protein        classes Cry1Ab, Cry1Ac, Cry1B, Cry1C, Cry1D, Cry1F, Cry2Ab,        Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP        1999141 and WO 2007/107302), or such proteins encoded by        synthetic genes as e.g. described in and U.S. patent application        Ser. No. 12/249,016; or    -   2) a crystal protein from Bacillus thuringiensis or a portion        thereof which is insecticidal in the presence of a second other        crystal protein from Bacillus thuringiensis or a portion        thereof, such as the binary toxin made up of the Cry34 and Cry35        crystal proteins (Moellenbeck et al. 2001, Nat. Biotechnol. 19:        668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71,        1765-1774) or the binary toxin made up of the Cry1A or Cry1F        proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5); or    -   3) a hybrid insecticidal protein comprising parts of different        insecticidal crystal proteins from Bacillus thuringiensis, such        as a hybrid of the proteins of 1) above or a hybrid of the        proteins of 2) above, e.g., the Cry1A.105 protein produced by        corn event MON89034 (WO 2007/027777); or    -   4) a protein of any one of 1) to 3) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation, such as the        Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A        protein in corn event MIR604; or    -   5) an insecticidal secreted protein from Bacillus thuringiensis        or Bacillus cereus, or an insecticidal portion thereof, such as        the vegetative insecticidal (VIP) proteins listed at:        http://www.lifesci.sussex.ac.uk/home/Neil_Crickmore/Bt/vip.html,        e.g., proteins from the VIP3Aa protein class; or    -   6) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a second        secreted protein from Bacillus thuringiensis or B. cereus, such        as the binary toxin made up of the VIP1A and VIP2A proteins (WO        94/21795); or    -   7) a hybrid insecticidal protein comprising parts from different        secreted proteins from Bacillus thuringiensis or Bacillus        cereus, such as a hybrid of the proteins in 1) above or a hybrid        of the proteins in 2) above; or    -   8) a protein of any one of 5) to 7) above wherein some,        particularly 1 to 10, amino acids have been replaced by another        amino acid to obtain a higher insecticidal activity to a target        insect species, and/or to expand the range of target insect        species affected, and/or because of changes introduced into the        encoding DNA during cloning or transformation (while still        encoding an insecticidal protein), such as the VIP3Aa protein in        cotton event COT102; or    -   9) a secreted protein from Bacillus thuringiensis or Bacillus        cereus which is insecticidal in the presence of a crystal        protein from Bacillus thuringiensis, such as the binary toxin        made up of VIP3 and Cry1A or Cry1F (U.S. Patent Appl. No.        61/126,083 and 61/195019), or the binary toxin made up of the        VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (U.S.        patent application Ser. No. 12/214,022 and EP 08010791.5).    -   10) a protein of 9) above wherein some, particularly 1 to 10,        amino acids have been replaced by another amino acid to obtain a        higher insecticidal activity to a target insect species, and/or        to expand the range of target insect species affected, and/or        because of changes introduced into the encoding DNA during        cloning or transformation (while still encoding an insecticidal        protein)

Of course, an insect-resistant transgenic plant, as used herein, alsoincludes any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 10. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 10, to expand the range oftarget insect species affected when using different proteins directed atdifferent target insect species, or to delay insect resistancedevelopment to the plants by using different proteins insecticidal tothe same target insect species but having a different mode of action,such as binding to different receptor binding sites in the insect.

An “insect-resistant transgenic plant”, as used herein, further includesany plant containing at least one transgene comprising a sequenceproducing upon expression a double-stranded RNA which upon ingestion bya plant insect pest inhibits the growth of this insect pest, asdescribed e.g. in WO 2007/080126, WO 2006/129204, WO 2007/074405, WO2007/080127 and WO 2007/035650.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

-   -   1) plants which contain a transgene capable of reducing the        expression and/or the activity of poly(ADP-ribose) polymerase        (PARP) gene in the plant cells or plants as described in WO        00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.    -   2) plants which contain a stress tolerance enhancing transgene        capable of reducing the expression and/or the activity of the        PARG encoding genes of the plants or plants cells, as described        e.g. in WO 2004/090140.    -   3) plants which contain a stress tolerance enhancing transgene        coding for a plant-functional enzyme of the nicotineamide        adenine dinucleotide salvage synthesis pathway including        nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic        acid mononucleotide adenyl transferase, nicotinamide adenine        dinucleotide synthetase or nicotine amide        phosphorybosyltransferase as described e.g. in EP 04077624.7, WO        2006/133827, PCT/EP07/002433, EP 1999263, or WO 2007/107326.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage-stability of theharvested product and/or altered properties of specific ingredients ofthe harvested product such as:

-   -   1) transgenic plants which synthesize a modified starch, which        in its physical-chemical characteristics, in particular the        amylose content or the amylose/amylopectin ratio, the degree of        branching, the average chain length, the side chain        distribution, the viscosity behaviour, the gelling strength, the        starch grain size and/or the starch grain morphology, is changed        in comparison with the synthesised starch in wild type plant        cells or plants, so that this is better suited for special        applications. Said transgenic plants synthesizing a modified        starch are disclosed, for example, in EP 0571427, WO 95/04826,        EP 0719338, WO 96/15248, WO 96/19581, WO 96/27674, WO 97/11188,        WO 97/26362, WO 97/32985, WO 97/42328, WO 97/44472, WO 97/45545,        WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654,        WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229,        WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO        2004/056999, WO 2005/030942, WO 2005/030941, WO 2005/095632, WO        2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO        2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823, WO        00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP        06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1, EP        07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO        2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145,        WO 99/12950, WO 99/66050, WO 99/53072, U.S. Pat. No. 6,734,341,        WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509,        WO 2005/002359, U.S. Pat. No. 5,824,790, U.S. Pat. No.        6,013,861, WO 94/04693, WO 94/09144, WO 94/11520, WO 95/35026,        WO 97/20936    -   2) transgenic plants which synthesize non starch carbohydrate        polymers or which synthesize non starch carbohydrate polymers        with altered properties in comparison to wild type plants        without genetic modification. Examples are plants producing        polyfructose, especially of the inulin and levan-type, as        disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460,        and WO 99/24593, plants producing alpha-1,4-glucans as disclosed        in WO 95/31553, US 2002031826, U.S. Pat. No. 6,284,479, U.S.        Pat. No. 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO        00/14249, plants producing alpha-1,6 branched alpha-1,4-glucans,        as disclosed in WO 00/73422, plants producing alternan, as        disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, U.S.        Pat. No. 5,908,975 and EP 0728213,    -   3) transgenic plants which produce hyaluronan, as for example        disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO        2007/039316, JP 2006304779, and WO 2005/012529.    -   4) transgenic plants or hybrid plants, such as onions with        characteristics such as high soluble solids content, ‘low        pungency’ (LP) and/or ‘long storage’ (LS), as described in U.S.        patent application Ser. No. 12/020,360 and 61/054,026.

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as cotton plants, with altered fibercharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants contain a mutation imparting such alteredfiber characteristics and include:

-   -   a) Plants, such as cotton plants, containing an altered form of        cellulose synthase genes as described in WO 98/00549    -   b) Plants, such as cotton plants, containing an altered form of        rsw2 or rsw3 homologous nucleic acids as described in WO        2004/053219    -   c) Plants, such as cotton plants, with increased expression of        sucrose phosphate synthase as described in WO 01/17333    -   d) Plants, such as cotton plants, with increased expression of        sucrose synthase as described in WO 02/45485    -   e) Plants, such as cotton plants, wherein the timing of the        plasmodesmatal gating at the basis of the fiber cell is altered,        e.g. through downregulation of fiber-selective (3-1,3-glucanase        as described in WO 2005/017157, or as described in EP 08075514.3        or U.S. Patent Appl. No. 61/128,938    -   f) Plants, such as cotton plants, having fibers with altered        reactivity, e.g. through the expression of        N-acetylglucosaminetransferase gene including nodC and chitin        synthase genes as described in WO 2006/136351

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered oil profile characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered oil profile characteristics and include:

-   -   a) Plants, such as oilseed rape plants, producing oil having a        high oleic acid content as described e.g. in U.S. Pat. No.        5,969,169, U.S. Pat. No. 5,840,946 or U.S. Pat. No. 6,323,392 or        U.S. Pat. No. 6,063,947    -   b) Plants such as oilseed rape plants, producing oil having a        low linolenic acid content as described in U.S. Pat. No.        6,270,828, U.S. Pat. No. 6,169,190, or U.S. Pat. No. 5,965,755    -   c) Plant such as oilseed rape plants, producing oil having a low        level of saturated fatty acids as described e.g. in U.S. Pat.        No. 5,434,283 or U.S. patent application Ser. No. 12/668,303

Plants or plant cultivars (that can be obtained by plant biotechnologymethods such as genetic engineering) which may also be treated accordingto the invention are plants, such as oilseed rape or related Brassicaplants, with altered seed shattering characteristics. Such plants can beobtained by genetic transformation, or by selection of plants contain amutation imparting such altered seed shattering characteristics andinclude plants such as oilseed rape plants with delayed or reduced seedshattering as described in U.S. Patent Appl. No. 61/135,230 WO09/068313and WO10/006732.

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, orcombination of transformation events, that are the subject of petitionsfor nonregulated status, in the United States of America, to the Animaland Plant Health Inspection Service (APHIS) of the United StatesDepartment of Agriculture (USDA) whether such petitions are granted orare still pending. At any time this information is readily availablefrom APHIS (4700 River Road Riverdale, Md. 20737, USA), for instance onits internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). Onthe filing date of this application the petitions for nonregulatedstatus that were pending with APHIS or granted by APHIS were those whichcontains the following information:

-   -   Petition: the identification number of the petition. Technical        descriptions of the transformation events can be found in the        individual petition documents which are obtainable from APHIS,        for example on the APHIS website, by reference to this petition        number. These descriptions are herein incorporated by reference.    -   Extension of Petition: reference to a previous petition for        which an extension is requested.    -   Institution: the name of the entity submitting the petition.    -   Regulated article: the plant species concerned.    -   Transgenic phenotype: the trait conferred to the plants by the        transformation event.    -   Transformation event or line: the name of the event or events        (sometimes also designated as lines or lines) for which        nonregulated status is requested.    -   APHIS documents: various documents published by APHIS in        relation to the Petition and which can be requested with APHIS.

Additional particularly useful plants containing single transformationevents or combinations of transformation events are listed for examplein the databases from various national or regional regulatory agencies(see for example http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php). Particularly useful transgenic plantswhich may be treated according to the invention are plants containingtransformation events, or a combination of transformation events, andthat are listed for example in the databases for various national orregional regulatory agencies including Event 1143-14A (cotton, insectcontrol, not deposited, described in WO 2006/128569); Event 1143-51B(cotton, insect control, not deposited, described in WO 2006/128570);Event 1445 (cotton, herbicide tolerance, not deposited, described inUS-A 2002-120964 or WO 02/034946); Event 17053 (rice, herbicidetolerance, deposited as PTA-9843, described in WO 2010/117737); Event17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO2010/117735); Event 281-24-236 (cotton, insect control-herbicidetolerance, deposited as PTA-6233, described in WO 2005/103266 or US-A2005-216969); Event 3006-210-23 (cotton, insect control-herbicidetolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO2005/103266); Event 3272 (corn, quality trait, deposited as PTA-9972,described in WO 2006/098952 or US-A 2006-230473); Event 40416 (corn,insect control-herbicide tolerance, deposited as ATCC PTA-11508,described in WO 2011/075593); Event 43A47 (corn, insectcontrol-herbicide tolerance, deposited as ATCC PTA-11509, described inWO 2011/075595); Event 5307 (corn, insect control, deposited as ATCCPTA-9561, described in WO 2010/077816); Event ASR-368 (bent grass,herbicide tolerance, deposited as ATCC PTA-4816, described in US-A2006-162007 or WO 2004/053062); Event B16 (corn, herbicide tolerance,not deposited, described in US-A 2003-126634); Event BPS-CV127-9(soybean, herbicide tolerance, deposited as NCIMB No. 41603, describedin WO 2010/080829); Event CE43-67B (cotton, insect control, deposited asDSM ACC2724, described in US-A 2009-217423 or WO2006/128573); EventCE44-69D (cotton, insect control, not deposited, described in US-A2010-0024077); Event CE44-69D (cotton, insect control, not deposited,described in WO 2006/128571); Event CE46-02A (cotton, insect control,not deposited, described in WO 2006/128572); Event COT102 (cotton,insect control, not deposited, described in US-A 2006-130175 or WO2004/039986); Event COT202 (cotton, insect control, not deposited,described in US-A 2007-067868 or WO 2005/054479); Event COT203 (cotton,insect control, not deposited, described in WO 2005/054480); EventDAS40278 (corn, herbicide tolerance, deposited as ATCC PTA-10244,described in WO 2011/022469); Event DAS-59122-7 (corn, insectcontrol-herbicide tolerance, deposited as ATCC PTA 11384, described inUS-A 2006-070139); Event DAS-59132 (corn, insect control-herbicidetolerance, not deposited, described in WO 2009/100188); Event DAS68416(soybean, herbicide tolerance, deposited as ATCC PTA-10442, described inWO 2011/066384 or WO 2011/066360); Event DP-098140-6 (corn, herbicidetolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 orWO 2008/112019); Event DP-305423-1 (soybean, quality trait, notdeposited, described in US-A 2008-312082 or WO 2008/054747); EventDP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158,described in US-A 2009-0210970 or WO 2009/103049); Event DP-356043-5(soybean, herbicide tolerance, deposited as ATCC PTA-8287, described inUS-A 2010-0184079 or WO 2008/002872); Event EE-1 (brinjal, insectcontrol, not deposited, described in WO 2007/091277); Event Fl117 (corn,herbicide tolerance, deposited as ATCC 209031, described in US-A2006-059581 or WO 98/044140); Event GA21 (corn, herbicide tolerance,deposited as ATCC 209033, described in US-A 2005-086719 or WO98/044140); Event GG25 (corn, herbicide tolerance, deposited as ATCC209032, described in US-A 2005-188434 or WO 98/044140); Event GHB119(cotton, insect control-herbicide tolerance, deposited as ATCC PTA-8398,described in WO 2008/151780); Event GHB614 (cotton, herbicide tolerance,deposited as ATCC PTA-6878, described in US-A 2010-050282 or WO2007/017186); Event GJ11 (corn, herbicide tolerance, deposited as ATCC209030, described in US-A 2005-188434 or WO 98/044140); Event GM RZ13(sugar beet, virus resistance, deposited as NCIMB-41601, described in WO2010/076212); Event H7-1 (sugar beet, herbicide tolerance, deposited asNCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO2004/074492); Event JOPLIN1 (wheat, disease tolerance, not deposited,described in US-A 2008-064032); Event LL27 (soybean, herbicidetolerance, deposited as NCIMB41658, described in WO 2006/108674 or US-A2008-320616); Event LL55 (soybean, herbicide tolerance, deposited asNCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); EventLLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343,described in WO 03/013224 or US-A 2003-097687); Event LLRICEO6 (rice,herbicide tolerance, deposited as ATCC-23352, described in U.S. Pat. No.6,468,747 or WO 00/026345); Event LLRICE601 (rice, herbicide tolerance,deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO00/026356); Event LY038 (corn, quality trait, deposited as ATCCPTA-5623, described in US-A 2007-028322 or WO 2005/061720); Event MIR162(corn, insect control, deposited as PTA-8166, described in US-A2009-300784 or WO 2007/142840); Event MIR604 (corn, insect control, notdeposited, described in US-A 2008-167456 or WO 2005/103301); EventMON15985 (cotton, insect control, deposited as ATCC PTA-2516, describedin US-A 2004-250317 or WO 02/100163); Event MON810 (corn, insectcontrol, not deposited, described in US-A 2002-102582); Event MON863(corn, insect control, deposited as ATCC PTA-2605, described in WO2004/011601 or US-A 2006-095986); Event MON87427 (corn, pollinationcontrol, deposited as ATCC PTA-7899, described in WO 2011/062904); EventMON87460 (corn, stress tolerance, deposited as ATCC PTA-8910, describedin WO 2009/111263 or US-A 2011-0138504); Event MON87701 (soybean, insectcontrol, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO2009/064652); Event MON87705 (soybean, quality trait-herbicidetolerance, deposited as ATCC PTA-9241, described in US-A 2010-0080887 orWO 2010/037016); Event MON87708 (soybean, herbicide tolerance, depositedas ATCC PTA9670, described in WO 2011/034704); Event MON87754 (soybean,quality trait, deposited as ATCC PTA-9385, described in WO 2010/024976);Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911,described in US-A 2011-0067141 or WO 2009/102873); Event MON88017 (corn,insect control-herbicide tolerance, deposited as ATCC PTA-5582,described in US-A 2008-028482 or WO 2005/059103); Event MON88913(cotton, herbicide tolerance, deposited as ATCC PTA-4854, described inWO 2004/072235 or US-A 2006-059590); Event MON89034 (corn, insectcontrol, deposited as ATCC PTA-7455, described in WO 2007/140256 or US-A2008-260932); Event MON89788 (soybean, herbicide tolerance, deposited asATCC PTA-6708, described in US-A 2006-282915 or WO 2006/130436); EventMS11 (oilseed rape, pollination control-herbicide tolerance, depositedas ATCC PTA-850 or PTA-2485, described in WO 01/031042); Event MS8(oilseed rape, pollination control-herbicide tolerance, deposited asATCC PTA-730, described in WO 01/041558 or US-A 2003-188347); EventNK603 (corn, herbicide tolerance, deposited as ATCC PTA-2478, describedin US-A 2007-292854); Event PE-7 (rice, insect control, not deposited,described in WO 2008/114282); Event RF3 (oilseed rape, pollinationcontrol-herbicide tolerance, deposited as ATCC PTA-730, described in WO01/041558 or US-A 2003-188347); Event RT73 (oilseed rape, herbicidetolerance, not deposited, described in WO 02/036831 or US-A2008-070260); Event T227-1 (sugar beet, herbicide tolerance, notdeposited, described in WO 02/44407 or US-A 2009-265817); Event T25(corn, herbicide tolerance, not deposited, described in US-A 2001-029014or WO 01/051654); Event T304-40 (cotton, insect control-herbicidetolerance, deposited as ATCC PTA-8171, described in US-A 2010-077501 orWO 2008/122406); Event T342-142 (cotton, insect control, not deposited,described in WO 2006/128568); Event TC1507 (corn, insectcontrol-herbicide tolerance, not deposited, described in US-A2005-039226 or WO 2004/099447); Event VIP1034 (corn, insectcontrol-herbicide tolerance, deposited as ATCC PTA-3925, described in WO03/052073), Event 32316 (corn, insect control-herbicide tolerance,deposited as PTA-11507, described in WO 2011/084632), Event 4114 (corn,insect control-herbicide tolerance, deposited as PTA-11506, described inWO 2011/084621).

Among the diseases of plants or crops that can be controlled by themethod according to the invention, mention can be made of:

Powdery mildew diseases such as:

-   -   Blumeria diseases, caused for example by Blumeria graminis;    -   Podosphaera diseases, caused for example by Podosphaera        leucotricha;    -   Sphaerotheca diseases, caused for example by Sphaerotheca        fuliginea;    -   Uncinula diseases, caused for example by Uncinula necator;        Rust diseases such as:    -   Gymnosporangium diseases, caused for example by Gymnosporangium        sabinae;    -   Hemileia diseases, caused for example by Hemileia vastatrix;    -   Phakopsora diseases, caused for example by Phakopsora pachyrhizi        or Phakopsora meibomiae;    -   Puccinia diseases, caused for example by Puccinia recondite,        Puccinia graminis or Puccinia striiformis;        Uromyces diseases, caused for example by Uromyces        appendiculatus;        Oomycete diseases such as:    -   Albugo diseases caused for example by Albugo candida;    -   Bremia diseases, caused for example by Bremia lactucae;    -   Peronospora diseases, caused for example by Peronospora pisi        or P. brassicae;    -   Phytophthora diseases, caused for example by Phytophthora        infestans;    -   Plasmopara diseases, caused for example by Plasmopara viticola;    -   Pseudoperonospora diseases, caused for example by        Pseudoperonospora humuli or Pseudoperonospora cubensis;    -   Pythium diseases, caused for example by Pythium ultimum;        Leafspot, leaf blotch and leaf blight diseases such as:    -   Alternaria diseases, caused for example by Alternaria solani;    -   Cercospora diseases, caused for example by Cercospora beticola;    -   Cladiosporum diseases, caused for example by Cladiosporium        cucumerinum;    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus (Conidiaform: Drechslera, Syn: Helminthosporium) or        Cochliobolus miyabeanus;    -   Colletotrichum diseases, caused for example by Colletotrichum        lindemuthanium;    -   Cycloconium diseases, caused for example by Cycloconium        oleaginum;    -   Diaporthe diseases, caused for example by Diaporthe citri;    -   Elsinoe diseases, caused for example by Elsinoe fawcettii;    -   Gloeosporium diseases, caused for example by Gloeosporium        laeticolor;    -   Glomerella diseases, caused for example by Glomerella cingulata;    -   Guignardia diseases, caused for example by Guignardia bidwelli;    -   Leptosphaeria diseases, caused for example by Leptosphaeria        maculans; Leptosphaeria nodorum;    -   Magnaporthe diseases, caused for example by Magnaporthe grisea;    -   Mycosphaerella diseases, caused for example by Mycosphaerella        graminicola; Mycosphaerella arachidicola; Mycosphaerella        fiiensis;    -   Phaeosphaeria diseases, caused for example by Phaeosphaeria        nodorum;    -   Pyrenophora diseases, caused for example by Pyrenophora teres,        or Pyrenophora tritici repentis;    -   Ramularia diseases, caused for example by Ramularia collocygni,        or Ramularia areola;    -   Rhynchosporium diseases, caused for example by Rhynchosporium        secalis;    -   Septoria diseases, caused for example by Septoria apii or        Septoria lycopercisi;    -   Typhula diseases, caused for example by Typhula incarnata;    -   Venturia diseases, caused for example by Venturia inaequalis;        Root, Sheath and stem diseases such as:    -   Corticium diseases, caused for example by Corticium graminearum;    -   Fusarium diseases, caused for example by Fusarium oxysporum;    -   Gaeumannomyces diseases, caused for example by Gaeumannomyces        graminis;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Sarocladium diseases caused for example by Sarocladium oryzae;    -   Sclerotium diseases caused for example by Sclerotium oryzae;    -   Tapesia diseases, caused for example by Tapesia acuformis;    -   Thielaviopsis diseases, caused for example by Thielaviopsis        basicola;        Ear and panicle diseases such as:    -   Alternaria diseases, caused for example by Alternaria spp.;    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Cladosporium diseases, caused for example by Cladosporium spp.;    -   Claviceps diseases, caused for example by Claviceps purpurea;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Monographella diseases, caused for example by Monographella        nivalis;        Smut and bunt diseases such as:    -   Sphacelotheca diseases, caused for example by Sphacelotheca        reiliana;    -   Tilletia diseases, caused for example by Tilletia caries;    -   Urocystis diseases, caused for example by Urocystis occulta;    -   Ustilago diseases, caused for example by Ustilago nuda;        Fruit rot and mould diseases such as:    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Botrytis diseases, caused for example by Botrytis cinerea;    -   Penicillium diseases, caused for example by Penicillium        expansum;    -   Rhizopus diseases caused by example by Rhizopus stolonifer    -   Sclerotinia diseases, caused for example by Sclerotinia        sclerotiorum;    -   Verticilium diseases, caused for example by Verticilium        alboatrum;        Seed and soilborne decay, mould, wilt, rot and damping-off        diseases:    -   Alternaria diseases, caused for example by Alternaria        brassicicola;    -   Aphanomyces diseases, caused for example by Aphanomyces        euteiches;    -   Ascochyta diseases, caused for example by Ascochyta lentis;    -   Aspergillus diseases, caused for example by Aspergillus flavus;    -   Cladosporium diseases, caused for example by Cladosporium        herbarum;    -   Cochliobolus diseases, caused for example by Cochliobolus        sativus;    -   (Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium);    -   Colletotrichum diseases, caused for example by Colletotrichum        coccodes;    -   Fusarium diseases, caused for example by Fusarium culmorum;    -   Gibberella diseases, caused for example by Gibberella zeae;    -   Macrophomina diseases, caused for example by Macrophomina        phaseolina;    -   Monographella diseases, caused for example by Monographella        nivalis;    -   Penicillium diseases, caused for example by Penicillium        expansum;    -   Phoma diseases, caused for example by Phoma lingam;    -   Phomopsis diseases, caused for example by Phomopsis sojae;    -   Phytophthora diseases, caused for example by Phytophthora        cactorum;    -   Pyrenophora diseases, caused for example by Pyrenophora        graminea;    -   Pyricularia diseases, caused for example by Pyricularia oryzae;    -   Pythium diseases, caused for example by Pythium ultimum;    -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;    -   Rhizopus diseases, caused for example by Rhizopus oryzae;    -   Sclerotium diseases, caused for example by Sclerotium rolfsii;    -   Septoria diseases, caused for example by Septoria nodorum;    -   Typhula diseases, caused for example by Typhula incarnata;    -   Verticillium diseases, caused for example by Verticillium        dahliae;        Canker, broom and dieback diseases such as:

Nectria diseases, caused for example by Nectria galligena;

Blight diseases such as:

-   -   Monilinia diseases, caused for example by Monilinia laxa;        Leaf blister or leaf curl diseases such as:    -   Exobasidium diseases caused for example by Exobasidium vexans;    -   Taphrina diseases, caused for example by Taphrina deformans;        Decline diseases of wooden plants such as:    -   Esca diseases, caused for example by Phaemoniella clamydospora;    -   Eutypa dyeback, caused for example by Eutypa lata;    -   Ganoderma diseases caused for example by Ganoderma boninense;    -   Rigidoporus diseases caused for example by Rigidoporus lignosus;        Diseases of Flowers and Seeds such as:    -   Botrytis diseases caused for example by Botrytis cinerea;        Diseases of Tubers such as:    -   Rhizoctonia diseases caused for example by Rhizoctonia solani;    -   Helminthosporium diseases caused for example by Helminthosporium        solani;        Club root diseases such as:    -   Plasmodiophora diseases, cause for example by Plamodiophora        brassicae;        Diseases caused by Bacterial Organisms such as:    -   Xanthomonas species for example Xanthomonas campestris pv.        oryzae;    -   Pseudomonas species for example Pseudomonas syringae pv.        lachrymans;    -   Erwinia species for example Erwinia amylovora.

The composition according to the invention may also be used againstfungal diseases liable to grow on or inside timber. The term “timber”means all types of species of wood, and all types of working of thiswood intended for construction, for example solid wood, high-densitywood, laminated wood, and plywood. The method for treating timberaccording to the invention mainly consists in contacting one or morecompounds according to the invention or a composition according to theinvention; this includes for example direct application, spraying,dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatmentaccording to the invention is generally and advantageously from 10 to800 g/ha, preferably from 50 to 300 g/ha for applications in foliartreatment. The dose of active substance applied is generally andadvantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to150 g per 100 kg of seed in the case of seed treatment. It is clearlyunderstood that the doses indicated herein are given as illustrativeexamples of the method according to the invention. A person skilled inthe art will know how to adapt the application doses, notably accordingto the nature of the plant or crop to be treated.

The compounds or mixtures according to the invention can also be usedfor the preparation of composition useful to curatively or preventivelytreat human or animal fungal diseases such as, for example, mycoses,dermatoses, trichophyton diseases and candidiases or diseases caused byAspergillus spp., for example Aspergillus fumigatus.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the control of phytopathogenic fungi.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the treatment of transgenic plants.

The present invention further relates to the use of compounds of theformula (I) as herein defined for the treatment of seed and of seed oftransgenic plants.

The present invention further relates to a process for producingcompositions for controlling phytopathogenic harmful fungi,characterized in that derivatives of the formula (I) as herein definedare mixed with extenders and/or surfactants.

The various aspects of the invention will now be illustrated withreference to the following table of compound examples and the followingpreparation or efficacy examples.

Table 1 illustrates in a non-limiting manner examples of compounds offormula (I) according to the invention:

In table 1, unless otherwise specified, M+H (Apcl+) means the molecularion peak plus 1 a.m.u. (atomic mass unit) as observed in massspectroscopy via positive atmospheric pressure chemical ionisation.

In table 1, the log P values were determined in accordance with EECDirective 79/831 Annex V.A8 by HPLC (High Performance LiquidChromatography) on a reversed-phase column (C 18), using the methoddescribed below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid andacetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile.

Calibration was carried out using unbranched alkan-2-ones (comprising 3to 16 carbon atoms) with known log P values (determination of the log Pvalues by the retention times using linear interpolation between twosuccessive alkanones). lambda-max-values were determined usingUV-spectra from 200 nm to 400 nm and the peak values of thechromatographic signals.

In table 1, “—” for Q¹ means direct bond.

TABLE 1 Example R¹ R² R³ T Z³ p n

Q¹ B logP Mass (M + H) NMR  1 CHF₂ Cl Me O H 1 0 — trifluoromethyl 2.39332 table 2  2 CHF₂ F Me O H 1 0 — trifluoromethyl 2.25 316 table 2  3CHF₂ H Me O 2-Bu 1 0 — pentafluoroethyl 3.69 404 table 2  4 CHF₂ Cl Me O2-Bu 1 0 — pentafluoroethyl 4.21 438 table 2  5 CHF₂ F Me O 2-Bu 1 0 —pentafluoroethyl 4.06 422 table 2  6 CHF₂ H Me O H 1 0 — hexyl 3.37 314table 2  7 CHF₂ Cl Me O H 1 0 — hexyl 3.94 348 table 2  8 CHF₂ F Me O H1 0 — hexyl 3.80 332 table 2  9 CHF₂ H Me O H 1 0 — cyclohexyl 2.88 312table 2 10 CHF₂ Cl Me O H 1 0 — cyclohexyl 3.48 346 table 2 11 CHF₂ F MeO H 1 0 — cyclohexyl 3.31 330 table 2 12 CHF₂ H Me O H 1 0 —adamantan-1-yl 3.89 364 table 2 13 CHF₂ Cl Me O H 1 0 — adamantan-1-yl4.67 398 table 2 14 CHF₂ F Me O H 1 0 — adamantan-1-yl 4.44 382 table 215 CHF₂ H Me O H 1 1 CH₂ — cyclohexyl 3.33 326 table 2 16 CHF₂ Cl Me O H1 1 CH₂ — cyclohexyl 3.89 360 table 2 17 CHF₂ F Me O H 1 1 CH₂ —cyclohexyl 3.78 344 table 2 18 CHF₂ Cl Me O H 2 0 — trifluoromethyl 2.80346 table 2 19 CHF₂ F Me O H 2 0 — trifluoromethyl 2.63 330 table 2 20CHF₂ H Me O H 2 0 — hexyl 3.71 328 table 2 21 CHF₂ Cl Me O H 2 0 — hexyl4.39 362 table 2 22 CHF₂ F Me O H 2 0 — hexyl 4.18 346 table 2 23 CHF₂Cl Me O H 2 0 — cyclohexyl 3.85 360 table 2 24 CHF₂ F Me O H 2 0 —cyclohexyl 3.60 344 table 2 25 CHF₂ H Me O H 2 0 — cyclohexyl 3.15 326table 2 26 CHF₂ F Me O H 2 1 CH₂ — cyclohexyl 4.19 358 27 CHF₂ H Me O H2 2 CH₂CH₂ O propyl 2.39 330 table 2 28 CHF₂ Cl Me O H 2 2 CH₂CH₂ Opropyl 2.90 364 table 2 29 CHF₂ F Me O H 2 2 CH₂CH₂ O propyl 2.73 348table 2 30 CHF₂ H Me O H 2 2 CH₂CH₂ O butyl 2.80 344 table 2 31 CHF₂ ClMe O H 2 2 CH₂CH₂ O butyl 3.35 378 table 2 32 CHF₂ F Me O H 2 2 CH₂CH₂ Obutyl 3.19 362 table 2 33 CHF₂ H Me O H 2 2 CH₂CH₂ O cyclopropylmethyl2.32 342 table 2 34 CHF₂ Cl Me O H 2 2 CH₂CH₂ O cyclopropylmethyl 2.82376 table 2 35 CHF₂ F Me O H 2 2 CH₂CH₂ O cyclopropylmethyl 2.66 360table 2 36 CHF₂ Cl Me O H 2 2 CH₂CH₂ O cyclobutylmethyl 3.51 390 table 237 CHF₂ F Me O H 2 2 CH₂CH₂ O cyclobutylmethyl 3.33 374 table 2 38 CHF₂H Me O H 2 2 CH₂CH₂ O cyclobutylmethyl 2.92 356 table 2 39 CHF₂ Cl Me OH 2 2 CH₂CH₂ O 3-methoxypropyl 2.39 394 table 2 40 CHF₂ F Me O H 2 2CH₂CH₂ O 3-methoxypropyl 2.25 378 table 2 41 CHF₂ H Me O H 2 2 CH₂CH₂ O3-methoxypropyl 1.96 360 table 2 42 CHF₂ H Me O H 2 2 CH₂CH₂ O2-cyclohexylethyl 4.23 398 table 2 43 CHF₂ Cl Me O H 2 2 CH₂CH₂ O2-cyclohexylethyl 4.87 432 table 2 44 CHF₂ F Me O H 2 2 CH₂CH₂ O2-cyclohexylethyl 4.67 416 table 2 45 CHF₂ H Me O H 2 3 (CH₂)₃ O methyl1.88 316 table 2 46 CHF₂ Cl Me O H 2 3 (CH₂)₃ O methyl 2.33 350 table 247 CHF₂ F Me O H 2 3 (CH₂)₃ O methyl 2.18 334 table 2 48 CHF₂ F Me O H 11 CH₂ — bicyclo[2.2.1]hept-2-yl 3.89 356 table 2 49 CHF₂ H Me O H 1 1CH₂ — bicyclo[2.2.1]hept-2-yl 3.44 338 table 2 50 CHF₂ Cl Me O H 1 1 CH₂— bicyclo[2.2.1]hept-2-yl 3.99 372 table 2 51 CHF₂ F Me S H 1 1 CH2 —cyclohexyl 3.96 360 table 2 52 CHF₂ F Me S H 1 0 — adamantan-1-yl 4.51398 table 2 Note: Me: methyl; 2-Bu: 2-butyl

Table 2 provides the NMR data (¹H) of a selected number of compoundsfrom table 1.

The ¹H-NMR data of selected examples are stated in the form of ¹H-NMRpeak lists. For each signal peak, the 6 value in ppm and the signalintensity in brackets are listed.

Intensity of sharp signals correlates with the height of the signals ina printed example of a NMR spectrum in cm and shows the real relationsof signal intensities. From broad signals several peaks or the middle ofthe signal and their relative intensity in comparison to the mostintensive signal in the spectrum can be shown.

The ¹H-NMR peak lists are similar to classical ¹H-NMR prints and containtherefore usually all peaks, which are listed at classicalNMR-interpretation. Additionally they can show like classical ¹H-NMRprints signals of solvents, stereoisomers of the target compounds, whichare also object of the invention, and/or peaks of impurities. To showcompound signals in the delta-range of solvents and/or water the usualpeaks of solvents, for example peaks of DMSO in DMSO-d6 and the peak ofwater are shown in our ¹H-NMR peak lists and have usually on average ahigh intensity.

The peaks of stereoisomers of the target compounds and/or peaks ofimpurities have usually on average a lower intensity than the peaks oftarget compounds (for example with a purity >90%). Such stereoisomersand/or impurities can be typical for the specific preparation process.Therefore their peaks can help to recognize the reproduction of ourpreparation process via “side-products-fingerprints”.

An expert, who calculates the peaks of the target compounds with knownmethods (MestreC, ACD-simulation, but also with empirically evaluatedexpectation values), can isolate the peaks of the target compounds asneeded optionally using additional intensity filters. This isolationwould be similar to relevant peak picking at classical ¹H-NMRinterpretation.

Further details of NMR-data description with peak lists can be found inthe publication “Citation of NMR Peaklist Data within PatentApplications” of the Research Disclosure Database Number 564025.

TABLE 2 NMR peak lists Example ¹H-NMR [DMSO-d6 - 400 Mhz]  1 7.1278(1.82); 6.9934 (3.52); 6.8590 (1.95); 5.0019 (0.43); 3.8798 (16.00);3.4223 (0.97); 3.4054 (1.56); 3.3899 (1.04); 3.3721 (0.40); 3.3300(18.04); 2.5063 (14.42); 2.5023 (19.55); 2.4985 (14.42); 2.2486 (0.39);2.2165 (0.62); 2.1985 (0.51); 2.0191 (0.56); 1.9831 (0.69); 1.9633(0.58); 1.9486 (0.60); 1.9319 (0.56); 1.9169 (0.38); 1.8342 (0.43);1.8272 (0.41)  2 7.1129 (1.74); 6.9784 (3.06); 6.8443 (1.84); 5.0119(0.48); 4.1438 (0.33); 3.8800 (0.64); 3.7811 (16.00); 3.6508 (1.07);3.4958 (0.66); 3.4769 (1.36); 3.4607 (0.94); 3.4508 (1.11); 3.4340(0.53); 3.3285 (24.88); 2.5020 (27.44); 2.2587 (0.47); 2.2371 (0.95);2.2183 (1.06); 2.1971 (0.76); 1.9785 (1.67); 1.9696 (1.86); 1.9520(1.08); 1.9376 (0.63); 1.8431 (0.67)  3 8.2431 (4.39); 7.1953 (1.74);7.0587 (2.92); 6.9233 (1.95); 3.8934 (16.00); 3.7632 (0.39); 3.7377(0.96); 3.7206 (0.72); 3.6408 (0.69); 3.6183 (1.28); 3.5992 (1.08);3.5747 (0.53); 3.3388 (68.28); 2.8909 (2.12); 2.8109 (0.65); 2.7797(1.05); 2.7585 (0.43); 2.7489 (0.54); 2.7310 (1.79); 2.5252 (0.74);2.5116 (13.80); 2.5074 (27.67); 2.5029 (36.71); 2.4984 (27.96); 2.4942(14.58); 2.3805 (0.32); 2.3588 (0.67); 2.3342 (0.68); 2.3248 (1.06);2.3020 (0.50); 2.1579 (0.48); 2.1409 (0.69); 2.1272 (0.79); 2.1063(0.50); 2.0938 (0.42); 1.8685 (0.56); 1.8584 (0.88); 1.8393 (1.63);1.8292 (0.97); 1.8194 (1.45); 1.7980 (0.71); 1.7431 (0.63); 1.7194(0.98); 1.7112 (1.09); 1.6890 (0.63); 1.6786 (0.57); 1.3616 (0.53);1.3494 (0.78); 1.3329 (1.18); 1.3205 (2.43); 1.3023 (2.35); 1.2844(1.47); 1.2665 (0.73); 1.2517 (0.34); 1.1439 (0.69); 1.1358 (0.61);1.1151 (0.53); 0.8946 (4.06); 0.8770 (7.89); 0.8591 (3.17); 0.0079(0.46); −0.0002 (11.61); −0.0084 (0.46)  4 7.0914 (1.81); 6.9569 (3.93);6.8224 (1.99); 3.8602 (16.00); 3.4756 (0.38); 3.4601 (1.09); 3.4489(1.17); 3.4415 (1.88); 3.4210 (1.49); 3.4020 (1.01); 3.3754 (0.43);3.3381 (47.06); 2.8910 (1.46); 2.8110 (0.71); 2.7798 (1.07); 2.7524(0.53); 2.7310 (1.24); 2.5251 (0.75); 2.5115 (11.78); 2.5073 (23.45);2.5028 (31.01); 2.4983 (23.61); 2.4943 (12.37); 2.3834 (0.33); 2.3628(0.73); 2.3470 (0.68); 2.3283 (1.21); 2.3068 (0.57); 2.2022 (0.49);2.1849 (0.75); 2.1693 (0.85); 2.1511 (0.51); 2.1355 (0.39); 1.8375(0.58); 1.8187 (0.86); 1.8076 (1.05); 1.7914 (1.22); 1.7710 (1.11);1.7499 (0.72); 1.7402 (0.50); 1.7187 (0.32); 1.6977 (0.51); 1.6713(0.98); 1.6407 (0.72); 1.3791 (0.49); 1.3713 (0.58); 1.3497 (1.28);1.3318 (2.03); 1.3097 (2.38); 1.2921 (2.09); 1.2759 (1.50); 1.2598(0.86); 1.2449 (0.58); 0.9077 (3.33); 0.8906 (7.22); 0.8732 (2.94);0.0079 (0.51); −0.0002 (13.95); −0.0084 (0.65)  5 7.0483 (2.09); 6.9127(3.29); 6.7786 (2.31); 3.7617 (16.00); 3.6881 (0.65); 3.6677 (1.33);3.6492 (0.87); 3.5103 (0.60); 3.4884 (1.23); 3.4673 (1.18); 3.4444(0.55); 3.3368 (56.07); 2.8908 (2.00); 2.8146 (0.87); 2.7834 (1.38);2.7621 (0.62); 2.7524 (0.71); 2.7306 (1.68); 2.5250 (0.87); 2.5115(16.60); 2.5071 (33.38); 2.5026 (44.20); 2.4981 (33.53); 2.4938 (17.41);2.3977 (0.40); 2.3741 (0.81); 2.3618 (0.71); 2.3392 (1.17); 2.3192(0.69); 2.1756 (0.77); 2.1641 (0.86); 2.1536 (0.96); 2.1292 (0.61);1.8666 (0.38); 1.8558 (0.69); 1.8466 (0.92); 1.8362 (1.17); 1.8285(1.30); 1.8178 (1.03); 1.8092 (1.29); 1.7869 (1.11); 1.7639 (0.79);1.7159 (0.78); 1.6937 (1.25); 1.6842 (1.36); 1.6628 (0.81); 1.6523(0.73); 1.3885 (0.38); 1.3706 (0.80); 1.3472 (1.49); 1.3360 (1.77);1.3283 (2.08); 1.3189 (1.60); 1.3104 (1.83); 1.2997 (1.82); 1.2814(1.38); 1.2637 (0.87); 1.2494 (0.49); 1.2352 (0.38); 1.1985 (0.36);1.1570 (0.83); 1.1480 (0.83); 1.1335 (0.70); 1.1266 (0.64); 0.8999(5.42); 0.8821 (10.80); 0.8643 (4.37); 0.0079 (0.80); −0.0002 (19.98);−0.0085 (0.78)  6 8.2316 (1.83); 7.3508 (0.47); 7.2151 (1.01); 7.0790(0.56); 4.0725 (0.63); 4.0510 (0.70); 3.9714 (0.62); 3.8992 (16.00);3.5533 (1.10); 3.5357 (1.14); 3.3495 (183.16); 2.8908 (2.23); 2.7308(1.86); 2.6723 (0.39); 2.5254 (1.25); 2.5120 (21.96); 2.5077 (43.95);2.5032 (58.32); 2.4987 (44.11); 2.4943 (22.94); 2.3301 (0.40); 1.9576(0.68); 1.9394 (1.19); 1.9216 (1.41); 1.9048 (1.18); 1.8871 (0.70);1.7902 (1.11); 1.7767 (0.96); 1.6288 (0.68); 1.6166 (0.66); 1.2591(7.00); 1.1101 (0.50); 0.8571 (3.70); 0.8414 (2.15); −0.0002 (1.14)  77.9520 (0.40); 7.1255 (0.38); 7.0982 (1.45); 6.9915 (0.76); 6.9636(2.91); 6.8571 (0.43); 6.8292 (1.55); 4.0682 (0.59); 4.0589 (0.88);4.0486 (1.11); 4.0394 (0.95); 3.9106 (0.52); 3.8881 (0.44); 3.8613(16.00); 3.6598 (0.38); 3.4749 (0.46); 3.4261 (0.48); 3.4056 (0.55);3.3481 (242.82); 3.2937 (0.76); 3.2754 (1.16); 3.2669 (1.15); 3.2585(1.03); 3.2496 (1.84); 3.2314 (1.28); 3.2115 (1.57); 3.1954 (1.23);3.1863 (0.85); 3.1689 (0.58); 2.8907 (2.97); 2.7305 (2.51); 2.6766(0.42); 2.6721 (0.57); 2.6676 (0.44); 2.5252 (1.65); 2.5116 (32.05);2.5074 (64.23); 2.5029 (85.27); 2.4984 (64.73); 2.4942 (33.73); 2.3339(0.44); 2.3297 (0.60); 2.3254 (0.46); 2.0077 (0.71); 1.9896 (1.01);1.9773 (0.83); 1.9603 (0.99); 1.9418 (0.68); 1.8778 (1.41); 1.8618(1.34); 1.8463 (1.35); 1.8309 (1.20); 1.8155 (0.68); 1.7392 (1.20);1.7226 (1.46); 1.7056 (1.51); 1.6885 (1.17); 1.6747 (1.15); 1.6587(1.47); 1.6448 (1.20); 1.6284 (1.02); 1.6156 (0.77); 1.5994 (0.35);1.3924 (0.74); 1.3708 (0.80); 1.3579 (0.83); 1.3352 (0.96); 1.2710(9.63); 1.2352 (1.94); 1.1720 (0.91); 1.1540 (1.03); 1.1360 (0.70);1.0382 (1.08); 1.0099 (0.89); 0.9919 (0.70); 0.9599 (0.57); 0.9177(0.33); 0.8993 (0.44); 0.8798 (2.88); 0.8646 (6.82); 0.8479 (3.10);0.8269 (1.64); 0.8091 (2.57); 0.7908 (1.16); −0.0002 (2.41)  8 7.9525(0.49); 7.1031 (1.27); 6.9683 (2.51); 6.8338 (1.35); 4.0329 (1.21);3.7674 (16.00); 3.4406 (1.51); 3.4313 (1.53); 3.4139 (1.36); 3.3464(253.25); 2.8908 (3.48); 2.7308 (2.93); 2.6767 (0.46); 2.6721 (0.61);2.6677 (0.47); 2.5115 (34.68); 2.5074 (68.02); 2.5029 (89.77); 2.4984(68.78); 2.4943 (36.92); 2.3342 (0.47); 2.3295 (0.63); 2.3252 (0.49);2.0366 (0.76); 2.0225 (1.11); 2.0067 (1.15); 1.9921 (1.05); 1.9746(0.57); 1.8887 (1.11); 1.8747 (1.39); 1.8597 (1.54); 1.8471 (1.43);1.7562 (1.18); 1.7438 (1.20); 1.7190 (1.18); 1.6990 (1.29); 1.6811(1.11); 1.6690 (1.00); 1.6502 (0.80); 1.6375 (0.93); 1.6236 (1.12);1.6084 (1.12); 1.5933 (1.06); 1.5761 (0.77); 1.5575 (0.36); 1.3870(0.52); 1.3658 (0.86); 1.3454 (1.12); 1.3338 (1.31); 1.2592 (12.67);1.0766 (1.11); 0.8591 (7.03); 0.8421 (4.10); −0.0002 (2.32)  9 8.2479(2.91); 7.3183 (0.97); 7.1822 (1.81); 7.0467 (1.03); 4.0828 (0.98);4.0691 (1.08); 3.9724 (0.74); 3.8967 (16.00); 3.5895 (0.36); 3.5640(0.91); 3.5469 (1.01); 3.5180 (0.57); 3.5007 (1.02); 3.4932 (0.89);3.4831 (0.61); 3.4751 (0.64); 3.4576 (0.33); 3.3584 (248.83); 3.2959(0.44); 2.8911 (2.40); 2.7308 (1.95); 2.6728 (0.42); 2.6685 (0.33);2.5262 (1.23); 2.5127 (22.46); 2.5083 (45.27); 2.5038 (60.19); 2.4992(45.53); 2.4949 (23.49); 2.3306 (0.41); 1.8682 (1.45); 1.8600 (1.40);1.8535 (1.47); 1.8370 (1.08); 1.7995 (0.81); 1.7730 (1.29); 1.7583(2.48); 1.7433 (2.30); 1.7086 (1.81); 1.6849 (1.84); 1.6245 (1.03);1.5638 (0.97); 1.5386 (1.56); 1.2348 (0.61); 1.1803 (0.52); 1.1151(1.92); 1.0941 (1.27); 1.0366 (0.86); 1.0056 (1.56); 0.9754 (1.19);0.9523 (0.39); −0.0002 (0.60) 10 7.9525 (0.35); 7.0928 (1.75); 6.9803(0.47); 6.9582 (3.16); 6.8237 (1.90); 4.0571 (0.57); 4.0432 (1.35);4.0284 (1.21); 4.0247 (1.21); 4.0103 (0.61); 3.9107 (0.44); 3.8814(2.88); 3.8616 (16.00); 3.4129 (0.48); 3.3513 (285.62); 3.2983 (0.72);3.2837 (0.69); 3.2738 (0.83); 3.2553 (1.54); 3.2459 (1.94); 3.2386(2.09); 3.2261 (2.41); 3.2066 (1.29); 3.1800 (0.43); 3.1465 (0.48);3.1291 (0.68); 3.1106 (0.54); 2.8910 (2.55); 2.7311 (2.18); 2.6767(0.45); 2.6725 (0.59); 2.6681 (0.46); 2.5077 (64.86); 2.5033 (85.61);2.4990 (65.84); 2.3344 (0.45); 2.3302 (0.61); 2.3255 (0.47); 1.8946(0.55); 1.8787 (1.05); 1.8577 (2.55); 1.8389 (2.67); 1.8178 (2.30);1.8038 (1.72); 1.7914 (1.40); 1.7837 (1.60); 1.7704 (1.56); 1.7613(1.35); 1.7544 (1.22); 1.7409 (2.31); 1.7278 (2.46); 1.7071 (2.52);1.6721 (1.30); 1.6611 (1.34); 1.6281 (3.80); 1.5985 (2.84); 1.5532(0.52); 1.5295 (0.50); 1.5223 (0.47); 1.5119 (0.66); 1.4751 (0.58);1.2463 (0.54); 1.2345 (1.36); 1.1996 (1.18); 1.1681 (1.71); 1.1351(2.63); 1.1126 (1.67); 1.0815 (0.74); 1.0473 (1.30); 1.0166 (2.47);0.9925 (1.93); 0.9864 (1.95); 0.9635 (0.75); 0.9557 (0.69); −0.0002(1.12) 11 7.1015 (1.97); 6.9662 (3.21); 6.8323 (2.14); 4.0771 (0.65);4.0606 (1.81); 4.0449 (1.77); 4.0278 (0.83); 3.7870 (1.21); 3.7641(16.00); 3.5102 (0.70); 3.4904 (1.34); 3.4697 (0.99); 3.3476 (246.60);3.3060 (1.27); 3.2873 (1.54); 3.2674 (1.36); 3.2458 (0.78); 2.8909(1.84); 2.7311 (1.52); 2.6766 (0.42); 2.6721 (0.57); 2.6675 (0.44);2.5253 (1.78); 2.5118 (31.52); 2.5075 (62.91); 2.5030 (83.09); 2.4985(62.66); 2.4943 (32.28); 2.3343 (0.44); 2.3298 (0.58); 2.3253 (0.44);1.8733 (1.33); 1.8611 (2.26); 1.8528 (2.76); 1.8379 (3.60); 1.8229(2.64); 1.7596 (0.76); 1.7428 (1.39); 1.7236 (2.73); 1.7081 (3.11);1.6928 (3.25); 1.6760 (2.06); 1.6509 (1.38); 1.6412 (1.42); 1.6288(2.31); 1.6059 (1.67); 1.5818 (1.60); 1.5314 (1.57); 1.4971 (1.38);1.2348 (0.93); 1.2139 (0.40); 1.1828 (0.84); 1.1494 (1.41); 1.1180(3.07); 1.0951 (1.99); 1.0701 (0.91); 1.0456 (0.92); 1.0182 (1.98);0.9886 (2.18); 0.9654 (1.14); 0.9580 (1.25); −0.0002 (1.45) 12 8.2685(3.24); 7.9526 (1.12); 7.2697 (1.07); 7.1333 (1.77); 6.9982 (1.14);4.1385 (1.06); 4.1268 (1.17); 4.1181 (0.87); 3.9737 (0.74); 3.9015(16.00); 3.6056 (0.46); 3.5910 (0.80); 3.5809 (0.78); 3.5700 (0.70);3.4808 (0.47); 3.4627 (0.86); 3.4541 (0.75); 3.4448 (0.57); 3.4366(0.78); 3.4177 (0.38); 3.3419 (99.54); 2.8908 (8.22); 2.7310 (6.75);2.6718 (0.37); 2.5473 (0.45); 2.5336 (0.41); 2.5252 (1.15); 2.5116(21.14); 2.5073 (41.89); 2.5028 (55.24); 2.4983 (41.67); 2.4941 (21.62);2.3296 (0.37); 1.9170 (4.34); 1.8766 (0.98); 1.8638 (1.04); 1.8516(1.05); 1.8383 (1.06); 1.8282 (0.99); 1.8099 (0.78); 1.7922 (0.36);1.7826 (0.35); 1.7329 (0.64); 1.6959 (1.41); 1.6585 (1.81); 1.6273(4.14); 1.5959 (4.15); 1.5590 (2.20); 1.5223 (4.45); 1.4991 (4.60);1.4690 (1.51); 1.2348 (0.56); −0.0002 (1.66) 13 7.1010 (1.72); 6.9653(2.39); 6.8320 (1.89); 4.0837 (0.95); 4.0704 (1.12); 4.0625 (1.30);4.0495 (1.04); 3.9106 (0.45); 3.8695 (16.00); 3.3457 (224.02); 3.3101(1.92); 3.2742 (0.57); 3.2104 (0.69); 3.1938 (0.86); 3.1863 (0.97);3.1694 (0.90); 3.1600 (0.71); 3.1433 (0.52); 2.9654 (0.47); 2.8908(2.10); 2.8813 (0.50); 2.7311 (1.60); 2.6767 (0.44); 2.6719 (0.60);2.6674 (0.48); 2.5253 (1.87); 2.5119 (33.88); 2.5075 (68.49); 2.5029(91.22); 2.4984 (69.34); 2.4940 (36.22); 2.3342 (0.47); 2.3298 (0.64);2.3253 (0.49); 1.9734 (0.53); 1.9301 (4.38); 1.8885 (0.93); 1.8690(1.18); 1.8542 (0.96); 1.8386 (0.77); 1.8148 (0.88); 1.8050 (1.12);1.7946 (1.25); 1.7839 (1.75); 1.7669 (1.34); 1.7597 (1.40); 1.7378(0.57); 1.7278 (0.43); 1.6683 (2.18); 1.6386 (4.26); 1.6021 (4.58);1.5722 (2.57); 1.5291 (12.31); 1.3865 (0.34); 1.2345 (0.83); −0.0002(1.89) 14 7.9524 (0.98); 7.1117 (1.73); 6.9759 (2.62); 6.8425 (1.88);4.1128 (1.21); 4.0996 (1.21); 4.0917 (1.71); 4.0788 (1.28); 3.7732(16.00); 3.5783 (0.71); 3.5527 (1.26); 3.5313 (0.90); 3.3947 (0.32);3.3434 (395.74); 3.2892 (0.58); 3.2675 (0.42); 3.2458 (0.85); 3.2195(1.29); 3.2046 (1.20); 3.1807 (0.63); 2.8906 (7.27); 2.7306 (6.03);2.6762 (0.81); 2.6717 (1.10); 2.6673 (0.84); 2.5249 (3.49); 2.5112(60.37); 2.5071 (119.91); 2.5026 (158.67); 2.4982 (120.53); 2.3339(0.79); 2.3293 (1.07); 2.3250 (0.82); 1.9192 (5.62); 1.8807 (0.82);1.8674 (1.06); 1.8597 (0.91); 1.8466 (1.25); 1.8298 (1.54); 1.7959(1.54); 1.7769 (1.91); 1.7500 (1.34); 1.7281 (0.53); 1.6606 (2.41);1.6304 (5.23); 1.5855 (5.95); 1.5576 (2.96); 1.4912 (14.88); 1.3868(0.42); 1.2801 (0.38); 1.2345 (1.13); −0.0002 (3.99) 15 8.2210 (3.40);7.9524 (0.44); 7.3551 (0.67); 7.2192 (1.37); 7.2006 (0.34); 7.0829(0.73); 4.2005 (0.88); 4.0701 (0.39); 3.9701 (0.77); 3.9081 (1.74);3.8956 (16.00); 3.5647 (1.04); 3.5396 (0.79); 3.5221 (1.12); 3.5065(0.95); 3.4457 (0.51); 3.3528 (230.67); 2.8910 (3.23); 2.7311 (2.73);2.6770 (0.35); 2.6726 (0.48); 2.6680 (0.38); 2.5621 (0.35); 2.5480(0.64); 2.5337 (0.60); 2.5255 (1.47); 2.5120 (26.55); 2.5079 (52.13);2.5034 (68.52); 2.4989 (51.79); 2.3345 (0.34); 2.3302 (0.47); 2.3258(0.36); 1.9797 (0.37); 1.9607 (1.02); 1.9423 (2.00); 1.9328 (1.99);1.9260 (2.23); 1.9090 (1.79); 1.8906 (1.01); 1.8415 (0.69); 1.8010(1.77); 1.7722 (1.28); 1.7301 (0.80); 1.6856 (2.18); 1.6553 (2.75);1.6116 (2.64); 1.5130 (0.66); 1.2805 (0.87); 1.2683 (0.82); 1.2341(1.47); 1.1959 (1.47); 1.1675 (2.77); 1.1425 (2.46); 1.1125 (1.54);0.9466 (0.70); 0.9209 (1.46); 0.8928 (1.28); −0.0002 (0.69) 16 7.9522(0.70); 7.1420 (0.67); 7.0965 (1.50); 7.0078 (1.38); 6.9620 (3.00);6.8736 (0.73); 6.8276 (1.60); 4.2000 (0.65); 4.1887 (0.91); 4.1788(1.03); 4.1692 (0.93); 4.1583 (0.72); 4.1487 (0.36); 3.9106 (0.60);3.8871 (0.55); 3.8693 (9.53); 3.8595 (16.00); 3.7222 (0.60); 3.4428(1.78); 3.4227 (1.25); 3.4028 (0.45); 3.3480 (421.10); 3.3049 (1.57);3.2867 (1.66); 3.2779 (1.57); 3.2692 (1.25); 3.2608 (2.06); 3.2431(1.17); 3.2161 (1.06); 3.1998 (1.67); 3.1840 (1.24); 3.1743 (1.09);3.1573 (0.81); 2.8909 (5.36); 2.7312 (4.37); 2.6765 (0.71); 2.6721(0.96); 2.6678 (0.73); 2.5254 (2.82); 2.5118 (52.22); 2.5076 (104.36);2.5031 (138.22); 2.4986 (104.50); 2.3343 (0.71); 2.3299 (0.97); 2.3253(0.72); 2.0330 (0.34); 2.0161 (0.88); 1.9981 (1.13); 1.9861 (1.13);1.9678 (1.32); 1.9491 (0.91); 1.9020 (1.69); 1.8871 (1.93); 1.8688(1.81); 1.8534 (1.50); 1.8376 (1.31); 1.8207 (0.92); 1.8038 (1.13);1.7656 (1.22); 1.7288 (2.37); 1.7151 (2.70); 1.6961 (3.95); 1.6844(4.13); 1.6666 (3.05); 1.6580 (2.99); 1.6320 (2.52); 1.6202 (3.12);1.6042 (2.20); 1.5917 (1.78); 1.5465 (0.58); 1.5118 (1.49); 1.4610(0.71); 1.4433 (0.70); 1.4275 (0.73); 1.4094 (0.69); 1.3866 (0.43);1.3612 (0.67); 1.3354 (1.12); 1.3289 (1.13); 1.2805 (1.48); 1.2340(2.85); 1.1980 (2.57); 1.1853 (2.23); 1.1653 (3.61); 1.1427 (2.34);1.1131 (1.14); 1.0788 (1.34); 1.0541 (2.15); 1.0277 (1.73); 1.0101(1.16); 0.9921 (0.64); 0.9535 (0.74); 0.9285 (1.58); 0.9158 (1.48);0.8990 (1.62); 0.8703 (0.71); 0.7377 (0.49); 0.7108 (0.40); 0.3419(0.42); 0.3136 (0.38); −0.0002 (2.32) 17 7.9519 (0.68); 7.1069 (1.46);6.9723 (2.89); 6.9462 (0.57); 6.8379 (1.57); 4.1655 (1.31); 3.7651(16.00); 3.4197 (2.78); 3.3900 (2.10); 3.3419 (219.06); 2.8907 (5.04);2.7306 (4.16); 2.6763 (0.52); 2.6718 (0.71); 2.6672 (0.54); 2.5480(0.49); 2.5249 (2.08); 2.5114 (39.48); 2.5071 (78.62); 2.5026 (103.93);2.4981 (78.62); 2.4939 (41.04); 2.3339 (0.55); 2.3295 (0.72); 2.3249(0.56); 2.0672 (0.40); 2.0497 (0.93); 2.0345 (1.27); 2.0186 (1.37);2.0039 (1.21); 1.9855 (0.65); 1.8976 (1.49); 1.8825 (1.74); 1.8668(1.88); 1.8524 (1.60); 1.7840 (1.35); 1.7467 (2.12); 1.7078 (3.83);1.6904 (3.95); 1.6798 (4.30); 1.6589 (3.44); 1.6136 (3.26); 1.5995(2.78); 1.5825 (2.66); 1.5678 (2.02); 1.5510 (1.67); 1.5327 (1.24);1.3868 (0.82); 1.3355 (0.63); 1.2803 (1.42); 1.2348 (3.15); 1.1851(2.74); 1.1619 (3.99); 1.1166 (1.66); 1.0698 (1.57); 0.9478 (0.99);0.9181 (2.10); 0.8896 (1.86); 0.8539 (0.77); −0.0002 (3.24) 18 7.1243(0.69); 6.9900 (1.36); 6.8556 (0.69); 5.3475 (0.46); 5.3282 (0.58);5.3069 (0.47); 5.3011 (0.58); 3.8843 (1.31); 3.8722 (16.00); 3.5818(0.57); 3.5470 (0.66); 3.3534 (0.34); 3.3302 (25.51); 3.1787 (0.34);3.1454 (0.57); 3.1160 (0.32); 2.5064 (20.48); 2.5022 (28.24); 2.4982(20.36); 2.0383 (0.58); 1.9994 (0.82); 1.7777 (0.41); 1.7433 (0.61);1.7312 (0.60); 1.7036 (0.97); 1.6728 (1.39); 1.6365 (0.99); 1.5988(0.74); 1.5651 (0.59); 1.3445 (0.59); 1.3123 (0.51); 1.2300 (0.49);0.8620 (0.35) 19 7.0737 (1.18); 7.0549 (0.36); 6.9395 (2.35); 6.8052(1.20); 5.3197 (0.53); 5.2999 (0.80); 5.2806 (0.51); 4.1446 (0.63);3.8722 (0.91); 3.8077 (0.73); 3.7938 (1.56); 3.7702 (16.00); 3.7431(0.47); 3.4343 (0.60); 3.3289 (50.72); 3.2136 (0.43); 3.1805 (0.74);3.1484 (0.43); 2.5242 (0.43); 2.5060 (35.18); 2.5020 (47.94); 2.4984(34.25); 2.0188 (0.81); 1.9858 (1.15); 1.7883 (0.62); 1.7683 (0.85);1.7544 (1.13); 1.7401 (1.03); 1.7050 (1.75); 1.6733 (1.89); 1.6051(0.99); 1.5737 (0.81); 1.4014 (0.37); 1.3699 (0.92); 1.3377 (0.87);1.3075 (0.38); 1.2298 (0.37); 0.8573 (0.45); −0.0002 (0.51) 20 7.9927(4.74); 7.1083 (1.75); 6.9726 (3.82); 6.8370 (1.94); 4.1015 (0.33);3.9468 (0.97); 3.8886 (16.00); 3.3463 (88.37); 2.8910 (2.05); 2.7314(1.70); 2.5255 (0.74); 2.5118 (14.01); 2.5076 (27.92); 2.5031 (36.96);2.4987 (28.11); 1.7370 (0.63); 1.7162 (0.77); 1.7016 (0.88); 1.6823(0.80); 1.6617 (0.58); 1.5689 (2.98); 1.4848 (0.48); 1.4661 (0.87);1.4494 (1.06); 1.4309 (0.97); 1.4144 (0.72); 1.3965 (0.38); 1.3463(0.48); 1.3361 (0.54); 1.3143 (0.95); 1.3041 (0.88); 1.2804 (1.24);1.2166 (4.26); 0.8579 (2.68); 0.8428 (5.97); 0.8254 (2.79); −0.0002(0.99) 21 7.9527 (0.35); 7.0825 (1.14); 6.9481 (2.42); 6.8138 (1.23);5.3003 (0.35); 4.6827 (0.58); 3.9107 (0.43); 3.8606 (16.00); 3.3694(0.77); 3.3440 (133.79); 3.2741 (0.82); 3.0604 (0.52); 2.8907 (2.66);2.7308 (2.41); 2.6760 (0.39); 2.6718 (0.51); 2.6672 (0.40); 2.5248(1.22); 2.5112 (27.79); 2.5071 (55.76); 2.5027 (74.51); 2.4982 (57.23);2.3338 (0.40); 2.3294 (0.55); 2.3253 (0.43); 1.7532 (0.58); 1.7203(0.48); 1.6333 (1.38); 1.6062 (2.16); 1.5458 (2.54); 1.4603 (0.69);1.3873 (0.42); 1.2471 (5.86); 1.2108 (2.12); 1.0284 (0.56); 1.0101(0.64); 0.9921 (0.37); 0.8528 (4.06); −0.0002 (2.10) 22 7.9524 (0.32);7.0428 (2.20); 6.9081 (4.67); 6.7735 (2.42); 3.7636 (16.00); 3.3538(199.77); 3.1679 (0.36); 3.0860 (0.35); 2.8911 (2.44); 2.7309 (2.09);2.6771 (0.38); 2.6725 (0.49); 2.6682 (0.37); 2.5258 (1.21); 2.5122(22.17); 2.5079 (44.34); 2.5034 (58.58); 2.4989 (44.16); 2.4947 (22.70);2.3301 (0.40); 1.7309 (0.80); 1.6200 (2.28); 1.5931 (3.08); 1.5595(1.96); 1.4695 (0.51); 1.4509 (0.91); 1.4351 (1.17); 1.4159 (1.11);1.3996 (0.80); 1.3870 (0.50); 1.2340 (4.73); 1.2290 (4.67); 1.0725(0.43); 1.0554 (0.44); 0.8574 (3.06); 0.8433 (5.86); 0.8261 (2.88);−0.0002 (1.19) 23 7.9522 (0.40); 7.0767 (1.04); 6.9422 (2.06); 6.8077(1.04); 5.2992 (0.39); 4.3402 (1.11); 4.3227 (1.02); 4.3124 (0.98);3.9106 (0.70); 3.8729 (3.52); 3.8676 (3.46); 3.8567 (16.00); 3.8285(0.51); 3.3564 (321.54); 3.3034 (2.04); 3.2745 (1.17); 3.2457 (0.79);3.2188 (0.64); 3.1734 (0.41); 3.1615 (0.45); 3.0486 (0.67); 3.0153(1.02); 2.9822 (0.59); 2.9657 (0.74); 2.8910 (3.22); 2.8814 (0.69);2.7309 (2.62); 2.6773 (0.58); 2.6727 (0.71); 2.6681 (0.58); 2.5259(1.83); 2.5124 (35.30); 2.5081 (71.08); 2.5036 (94.36); 2.4991 (71.29);2.4947 (36.67); 2.3347 (0.51); 2.3303 (0.69); 2.3259 (0.53); 1.8791(1.16); 1.8397 (2.11); 1.8029 (1.84); 1.7903 (1.57); 1.7496 (1.77);1.7046 (3.53); 1.6726 (3.07); 1.6253 (2.09); 1.6000 (2.17); 1.5233(2.63); 1.5124 (2.90); 1.3896 (1.10); 1.3777 (0.93); 1.3661 (1.08);1.3557 (1.41); 1.3443 (1.19); 1.3352 (0.93); 1.3219 (1.02); 1.3109(1.04); 1.2803 (1.06); 1.2622 (1.26); 1.2465 (1.30); 1.2340 (2.44);1.2038 (1.51); 1.1688 (1.89); 1.1398 (1.83); 1.1073 (0.86); 1.0280(0.50); 1.0100 (0.63); 0.9915 (0.54); 0.9628 (0.63); 0.9298 (1.16);0.8968 (1.54); 0.8852 (1.23); 0.8583 (0.93); 0.8307 (0.33); −0.0002(1.10) 24 7.9521 (0.62); 7.0387 (3.14); 6.9037 (6.67); 6.7693 (3.36);4.3054 (1.67); 4.2808 (1.66); 3.7887 (1.63); 3.7587 (16.00); 3.7240(0.60); 3.5387 (1.11); 3.5078 (1.32); 3.4452 (0.36); 3.3563 (648.70);3.2484 (0.52); 3.1677 (0.79); 3.0732 (1.03); 3.0410 (1.66); 3.0118(0.90); 2.8910 (5.02); 2.7306 (4.04); 2.6818 (0.75); 2.6772 (1.03);2.6727 (1.29); 2.6680 (1.04); 2.6631 (0.77); 2.6545 (0.74); 2.6226(0.41); 2.5617 (0.73); 2.5478 (1.43); 2.5338 (1.46); 2.5259 (3.49);2.5211 (5.25); 2.5125 (57.69); 2.5081 (116.61); 2.5035 (155.00); 2.4989(115.84); 2.4945 (57.97); 2.3348 (0.79); 2.3302 (1.07); 2.3257 (0.80);1.8783 (2.42); 1.8440 (3.25); 1.8003 (2.13); 1.7586 (1.42); 1.7203(1.60); 1.6730 (2.76); 1.6517 (3.02); 1.6056 (4.18); 1.5947 (4.63);1.5705 (5.01); 1.4664 (0.78); 1.4360 (1.43); 1.3869 (1.29); 1.3761(0.96); 1.3545 (1.60); 1.3205 (1.31); 1.2922 (1.47); 1.2804 (1.57);1.2539 (1.78); 1.2342 (2.69); 1.1974 (1.93); 1.1678 (2.14); 1.1436(2.22); 1.1218 (1.47); 1.0906 (0.85); 1.0553 (0.47); 1.0379 (0.38);1.0033 (0.51); 0.9743 (0.44); 0.9350 (0.58); 0.9076 (1.16); 0.8759(1.47); 0.8478 (1.42); 0.8145 (1.00); 0.7819 (0.43); 0.7408 (0.50);0.7140 (0.44); 0.5474 (0.48); 0.5165 (0.44); −0.0002 (0.96) 25 8.0248(2.40); 7.9679 (0.85); 7.9528 (1.42); 7.1074 (2.50); 6.9718 (5.26);6.8360 (2.71); 4.3169 (1.34); 3.8876 (16.00); 3.6119 (0.85); 3.5816(0.94); 3.5104 (0.47); 3.3439 (173.06); 3.0408 (0.61); 3.0087 (1.01);2.9778 (0.61); 2.8906 (6.93); 2.7307 (5.92); 2.6717 (0.63); 2.6674(0.57); 2.6314 (0.41); 2.5072 (52.92); 2.5028 (69.05); 2.4984 (53.42);2.3336 (0.37); 2.3295 (0.49); 2.3254 (0.39); 1.8215 (2.86); 1.6573(2.92); 1.6002 (3.81); 1.5647 (4.44); 1.3356 (1.62); 1.2338 (1.28);1.2190 (1.50); 1.1863 (1.93); 1.1552 (2.21); 1.0287 (0.45); 0.9082(0.91); 0.8800 (1.15); 0.8565 (1.14); 0.8318 (0.84); 0.6740 (0.40);0.6476 (0.39); 0.5822 (0.38); 0.5583 (0.34); −0.0002 (37.37) 27 8.0063(5.01); 7.9522 (0.40); 7.1312 (1.53); 6.9955 (3.31); 6.8599 (1.68);3.9454 (1.03); 3.9084 (0.85); 3.8995 (0.57); 3.8836 (16.00); 3.3962(0.43); 3.3522 (163.91); 3.3151 (1.41); 3.2891 (1.50); 3.2188 (1.42);2.8908 (2.92); 2.7308 (2.38); 2.6724 (0.37); 2.5256 (0.90); 2.5122(18.41); 2.5078 (36.91); 2.5033 (48.76); 2.4988 (36.67); 2.4945 (18.84);2.3300 (0.33); 1.9876 (0.34); 1.9718 (0.73); 1.9512 (1.03); 1.9364(1.15); 1.9157 (0.91); 1.9000 (0.41); 1.7733 (0.46); 1.7568 (1.24);1.7402 (1.44); 1.7221 (1.23); 1.7054 (0.97); 1.6891 (0.46); 1.5875(2.88); 1.5439 ( 1.15); 1.4222 (0.96); 1.3527 (0.53); 1.3414 (0.48);1.3205 (0.82); 1.3100 (0.65); 1.2882 (0.64); 1.2803 (0.53); 1.2347(0.56); 0.8019 (2.36); −0.0002 (0.61) 28 7.9520 (0.41); 7.0942 (1.28);6.9598 (2.73); 6.8254 (1.38); 4.7911 (0.45); 3.9106 (0.34); 3.8568(16.00); 3.3508 (237.98); 3.2945 (2.17); 3.2170 (0.81); 3.1403 (0.83);2.8910 (2.97); 2.7312 (2.64); 2.6723 (0.53); 2.5076 (56.42); 2.5032(74.35); 2.4989 (56.82); 2.3299 (0.52); 1.9562 (0.40); 1.8541 (0.32);1.7531 (0.76); 1.6176 (1.67); 1.5593 (1.65); 1.5196 (1.31); 1.5014(1.26); 1.4841 (1.12); 1.3116 (0.71); 1.2807 (0.73); 1.2469 (0.63);1.2349 (0.97); 1.2290 (0.76); 0.8621 (1.56); 0.8515 (1.87); 0.7430(0.73); −0.0002 (0.96) 29 7.9519 (0.38); 7.0576 (1.71); 6.9230 (3.61);6.7884 (1.86); 3.7611 (16.00); 3.3419 (124.18); 3.3032 (1.42); 3.2770(1.44); 3.2606 (1.48); 2.8903 (2.75); 2.7303 (2.41); 2.6712 (0.45);2.6668 (0.36); 2.5067 (48.99); 2.5023 (64.42); 2.4979 (49.49); 2.3291(0.45); 1.9286 (0.65); 1.7725 (0.52); 1.7558 (1.40); 1.7392 (1.66);1.7214 (1.43); 1.7046 (1.12); 1.6882 (0.66); 1.6484 (1.72); 1.6202(3.20); 1.5708 (1.93); 1.4523 (0.71); 1.3867 (0.61); 1.2946 (0.87);1.2800 (0.83); 1.2628 (0.71); 1.2345 (0.89); 0.8099 (1.54); −0.0002(1.67) 30 8.0053 (5.00); 7.9524 (0.40); 7.1303 (1.56); 6.9946 (3.39);6.8590 (1.71); 4.0957 (0.35); 3.9460 (1.02); 3.9082 (0.92); 3.8847(16.00); 3.3455 (177.01); 3.2749 (2.18); 2.8906 (2.93); 2.7306 (2.40);2.6763 (0.37); 2.6718 (0.49); 2.6674 (0.38); 2.5251 (1.29); 2.5116(25.05); 2.5073 (50.07); 2.5028 (66.21); 2.4983 (49.89); 2.4939 (25.60);2.3340 (0.34); 2.3295 (0.46); 2.3252 (0.35); 1.9812 (0.34); 1.9655(0.71); 1.9449 (1.02); 1.9300 (1.13); 1.9094 (0.91); 1.8934 (0.40);1.7681 (0.46); 1.7519 (1.21); 1.7352 (1.40); 1.7172 (1.21); 1.7004(0.95); 1.6839 (0.47); 1.5847 (2.92); 1.3863 (1.12); 1.3518 (0.91);1.3188 (1.05); 1.3080 (0.90); 1.2802 (1.17); 1.2505 (1.21); 1.2348(1.54); 0.8650 (4.18); 0.8467 (7.72); 0.8285 (3.50); −0.0002 (1.46) 317.0928 (1.26); 6.9583 (2.67); 6.8240 (1.35); 4.7842 (0.42); 3.9107(0.33); 3.8575 (16.00); 3.3466 (135.64); 3.1957 (0.91); 3.1102 (0.46);2.8908 (2.44); 2.7310 (2.07); 2.6718 (0.48); 2.5251 (1.31); 2.5115(25.50); 2.5073 (51.19); 2.5028 (67.94); 2.4983 (51.61); 2.4942 (27.08);2.3339 (0.35); 2.3294 (0.47); 2.3252 (0.37); 1.9510 (0.38); 1.8532(0.33); 1.7476 (0.72); 1.6160 (1.57); 1.5573 (1.54); 1.4988 (0.73);1.4615 (1.11); 1.3866 (0.32); 1.2999 (1.71); 1.2809 (1.50); 1.2469(0.78); 1.2350 (1.07); 1.2105 (0.49); 1.1756 (0.42); 0.9002 (0.60);0.8820 (1.95); 0.8635 (2.69); −0.0002 (1.99) 32 7.9521 (0.34); 7.0563(1.89); 6.9216 (4.01); 6.7871 (2.06); 3.7625 (16.00); 3.3585 (223.49);3.3056 (1.82); 3.1678 (0.86); 2.8912 (2.75); 2.7316 (2.24); 2.6729(0.43); 2.5261 (1.23); 2.5212 (1.87); 2.5126 (21.70); 2.5082 (43.65);2.5037 (57.75); 2.4991 (43.26); 2.4948 (21.94); 2.3304 (0.39); 1.9208(0.63); 1.7688 (0.54); 1.7522 (1.46); 1.7357 (1.72); 1.7177 (1.47);1.7010 (1.17); 1.6844 (0.69); 1.6466 (1.72); 1.6179 (3.14); 1.5704(1.87); 1.4159 (0.68); 1.3869 (0.69); 1.2907 (1.59); 1.2806 (1.64);1.2633 (1.49); 1.2348 (1.52); 0.8639 (3.11); 0.8458 (5.39); 0.8278(2.68); −0.0002 (0.69) 33 8.0211 (3.06); 7.9527 (0.37); 7.1336 (1.28);6.9979 (2.71); 6.8623 (1.37); 3.9473 (1.11); 3.9087 (0.95); 3.8881(16.00); 3.3439 (113.46); 3.1208 (1.28); 2.8909 (2.71); 2.7310 (2.24);2.6722 (0.39); 2.5251 (1.23); 2.5117 (20.58); 2.5075 (40.52); 2.5030(53.20); 2.4985 (40.10); 2.4944 (20.71); 2.3297 (0.33); 2.0024 (0.34);1.9869 (0.71); 1.9810 (0.46); 1.9660 (0.99); 1.9514 (1.11); 1.9358(0.54); 1.9303 (0.86); 1.9147 (0.37); 1.7662 (0.43); 1.7500 (1.17);1.7332 (1.37); 1.7154 (1.20); 1.6984 (0.95); 1.6822 (0.48); 1.6467(0.63); 1.5831 (2.90); 1.5442 (1.16); 1.3533 (0.35); 1.3433 (0.34);1.3216 (0.73); 1.3112 (0.58); 1.2895 (0.59); 1.2807 (0.51); 1.2350(0.56); 0.9029 (0.50); 0.4223 (2.70); 0.4024 (2.50); 0.0934 (1.63);0.0001 (1.10) 34 7.9523 (0.36); 7.0960 (0.85); 6.9615 (1.75); 6.8271(0.90); 4.7995 (0.44); 3.9110 (0.37); 3.8595 (16.00); 3.3584 (274.37);3.2994 (1.11); 3.2268 (1.11); 3.2100 (1.09); 3.1791 (1.25); 3.1680(1.22); 3.1069 (0.62); 3.0767 (0.52); 3.0507 (0.57); 2.8914 (2.85);2.7314 (2.34); 2.6777 (0.34); 2.6731 (0.46); 2.6685 (0.36); 2.5263(1.17); 2.5128 (24.62); 2.5085 (50.00); 2.5039 (66.77); 2.4994 (50.64);2.4951 (26.34); 2.3352 (0.35); 2.3306 (0.48); 2.3261 (0.37); 1.9634(0.39); 1.8255 (0.33); 1.7525 (0.65); 1.6329 (1.45); 1.6187 (1.54);1.5600 (1.61); 1.2805 (0.63); 1.2470 (0.62); 1.2349 (0.96); 1.2293(0.81); 1.2106 (0.33); 1.0102 (0.33); 0.9917 (0.36); 0.9643 (0.44);0.4228 (1.37); 0.1698 (0.61); 0.1580 (0.96); 0.1471 (1.07); 0.0365(0.33); 0.0001 (0.78) 35 7.9522 (0.40); 7.0584 (1.58); 6.9237 (3.31);6.7892 (1.70); 3.7644 (16.00); 3.3548 (211.17); 3.1677 (1.15); 3.1415(1.24); 2.8911 (3.16); 2.7309 (2.57); 2.6772 (0.35); 2.6726 (0.46);2.6682 (0.35); 2.5260 (1.19); 2.5124 (23.21); 2.5080 (46.69); 2.5035(61.78); 2.4990 (46.45); 2.4946 (23.78); 2.3348 (0.34); 2.3303 (0.45);2.3258 (0.34); 1.9406 (0.79); 1.7626 (0.52); 1.7459 (1.29); 1.7293(1.55); 1.7116 (1.39); 1.6946 (1.18); 1.6777 (0.74); 1.6490 (1.81);1.6211 (3.37); 1.5723 (2.02); 1.2939 (0.77); 1.2807 (0.79); 1.2635(0.69); 1.2349 (0.89); 0.9316 (0.36); 0.4171 (2.31); 0.4007 (2.14);0.0985 (1.06); −0.0000 (0.90) 36 7.9520 (0.36); 7.0948 (1.41); 6.9603(3.04); 6.8259 (1.54); 4.7919 (0.44); 3.9107 (0.39); 3.8576 (16.00);3.3461 (150.34); 3.2254 (0.80); 3.1462 (0.74); 2.8906 (2.94); 2.7306(2.38); 2.6719 (0.41); 2.5251 (1.23); 2.5117 (23.00); 2.5073 (46.09);2.5028 (61.23); 2.4982 (46.25); 2.4938 (23.79); 2.3339 (0.45); 2.3295(0.56); 2.3249 (0.49); 1.9533 (1.31); 1.8893 (0.79); 1.8489 (1.28);1.8399 (1.26); 1.8260 (1.41); 1.8060 (1.38); 1.7466 (1.21); 1.7231(1.29); 1.7009 (1.38); 1.6737 (1.44); 1.6579 (1.49); 1.6208 (1.82);1.5526 (1.85); 1.3353 (0.35); 1.2801 (0.63); 1.2464 (0.61); 1.2346(1.01); 1.2288 (0.74); −0.0002 (1.32) 37 7.0580 (1.81); 6.9234 (3.83);6.7889 (1.97); 3.7624 (16.00); 3.3460 (169.03); 3.3027 (1.75); 2.8905(1.92); 2.7305 (1.66); 2.6760 (0.34); 2.6718 (0.45); 2.6672 (0.36);2.5112 (23.72); 2.5071 (46.91); 2.5027 (62.11); 2.4982 (47.33); 2.4940(24.80); 2.3339 (0.49); 2.3295 (0.61); 2.3252 (0.50); 1.9175 (1.83);1.8542 (0.75); 1.8293 (1.07); 1.8084 (1.50); 1.7871 (1.47); 1.7763(1.45); 1.7598 (2.08); 1.7430 (2.04); 1.7252 (1.68); 1.7083 (1.34);1.6911 (1.01); 1.6486 (2.40); 1.6219 (3.78); 1.5910 (2.03); 1.5675(2.21); 1.2904 (0.70); 1.2803 (0.75); 1.2615 (0.65); 1.2347 (0.89);−0.0002 (1.39) 38 8.0032 (5.03); 7.9524 (0.37); 7.1304 (1.60); 6.9948(3.45); 6.8592 (1.75); 3.9463 (1.12); 3.9085 (0.94); 3.8993 (0.68);3.8854 (16.00); 3.3475 (130.76); 3.3073 (1.46); 3.2905 (1.51); 3.2563(1.64); 2.8909 (2.80); 2.7311 (2.27); 2.6723 (0.37); 2.5254 (1.03);2.5118 (19.24); 2.5076 (37.77); 2.5031 (49.43); 2.4986 (37.23); 2.4944(19.29); 2.4045 (0.40); 2.3983 (0.40); 2.3343 (0.34); 2.3299 (0.42);2.3254 (0.33); 1.9805 (0.41); 1.9646 (0.94); 1.9593 (0.81); 1.9440(1.69); 1.9292 (2.22); 1.9088 (2.08); 1.8937 (1.27); 1.8550 (0.53);1.8482 (0.52); 1.8288 (0.99); 1.8086 (1.66); 1.7872 (1.55); 1.7715(1.36); 1.7555 (1.75); 1.7387 (1.70); 1.7208 (1.36); 1.7040 (1.07);1.6872 (0.64); 1.6143 (2.51); 1.5892 (3.39); 1.3503 (0.36); 1.3193(0.74); 1.3092 (0.59); 1.2867 (0.60); 1.2812 (0.53); 1.2349 (0.61);−0.0002 (0.89) 39 7.9518 (0.41); 7.0944 (1.17); 6.9600 (2.50); 6.8256(1.27); 4.7858 (0.42); 3.9105 (0.33); 3.8590 (16.00); 3.3437 (95.91);3.2189 (2.43); 3.1969 (10.69); 3.1081 (0.44); 2.8903 (3.09); 2.7303(2.64); 2.6759 (0.35); 2.6714 (0.47); 2.6669 (0.37); 2.5245 (1.42);2.5109 (26.08); 2.5068 (51.42); 2.5023 (67.59); 2.4978 (51.02); 2.4935(26.35); 2.3290 (0.47); 1.9578 (0.37); 1.7455 (0.93); 1.7294 (1.14);1.7132 (1.37); 1.7032 (1.39); 1.6133 (1.66); 1.5601 (1.93); 1.2803(0.60); 1.2461 (0.61); 1.2347 (0.90); 1.2284 (0.76); −0.0002 (2.07) 407.0577 (1.06); 6.9231 (2.28); 6.7886 (1.17); 3.7636 (8.56); 3.3413(74.55); 3.2951 (1.28); 3.1900 (16.00); 2.8906 (1.75); 2.7308 (1.47);2.6715 (0.34); 2.5247 (1.00); 2.5111 (18.57); 2.5069 (36.74); 2.5024(48.43); 2.4979 (36.65); 1.7578 (0.75); 1.7411 (0.90); 1.7232 (0.84);1.7063 (0.75); 1.6898 (0.63); 1.6141 (1.87); 1.5706 (1.29); 1.2929(0.38); 1.2807 (0.41); 1.2625 (0.35); 1.2350 (0.50); −0.0002 (1.49) 418.0028 (3.16); 7.1307 (1.03); 6.9951 (2.24); 6.8595 (1.13); 3.9481(0.67); 3.9083 (0.52); 3.8989 (0.41); 3.8860 (9.96); 3.3469 (98.85);3.3188 (1.78); 3.3005 (1.97); 3.2919 (1.97); 3.1897 (16.00); 2.8907(1.50); 2.7307 (1.23); 2.5252 (0.71); 2.5117 (12.14); 2.5074 (24.31);2.5029 (32.36); 2.4984 (24.57); 2.4942 (12.65); 1.9639 (0.39); 1.9437(0.58); 1.9285 (0.63); 1.9083 (0.50); 1.7579 (0.73); 1.7413 (0.85);1.7231 (0.75); 1.7064 (0.62); 1.6897 (0.41); 1.6144 (1.34); 1.5782(1.99); 1.5434 (0.76); 1.3195 (0.46); 1.3093 (0.35); 1.2871 (0.37);1.2346 (0.36); −0.0002 (0.59) 42 8.0004 (4.99); 7.9521 (0.35); 7.1267(1.67); 6.9910 (3.67); 6.8554 (1.86); 3.9464 (1.09); 3.9084 (0.74);3.8988 (0.50); 3.8847 (16.00); 3.3571 (225.79); 3.3149 (2.08); 3.2886(2.60); 3.1679 (0.33); 2.8910 (2.52); 2.7319 (2.00); 2.7307 (2.10);2.6772 (0.34); 2.6727 (0.44); 2.6682 (0.34); 2.5261 (1.29); 2.5124(22.47); 2.5082 (44.83); 2.5036 (58.98); 2.4991 (44.48); 2.4949 (22.97);2.3304 (0.41); 1.9547 (0.69); 1.9344 (0.97); 1.9190 (1.09); 1.8988(0.85); 1.8829 (0.37); 1.7748 (0.45); 1.7588 (1.15); 1.7420 (1.33);1.7241 (1.14); 1.7072 (0.88); 1.6907 (0.47); 1.6346 (3.79); 1.6088(6.10); 1.5766 (3.84); 1.3179 (1.80); 1.3079 (1.83); 1.2868 (1.86);1.2348 (1.18); 1.2107 (0.68); 1.1788 (1.12); 1.1459 (1.75); 1.1264(2.19); 1.1099 (1.21); 1.0765 (0.55); 0.8792 (0.76); 0.8523 (1.65);0.8263 (1.31); 0.8003 (0.47); −0.0002 (1.12) 43 7.9520 (0.39); 7.0894(1.21); 6.9548 (2.57); 6.8205 (1.31); 4.7810 (0.43); 3.9105 (0.35);3.8575 (16.00); 3.4438 (0.56); 3.4282 (0.55); 3.4132 (0.70); 3.4039(0.72); 3.3964 (1.03); 3.3881 (1.66); 3.3514 (222.81); 3.2494 (0.90);3.2209 (1.14); 3.1061 (0.58); 2.8910 (2.80); 2.7310 (2.37); 2.6724(0.43); 2.6678 (0.34); 2.5077 (46.92); 2.5033 (61.45); 2.4989 (46.81);2.3343 (0.34); 2.3300 (0.45); 1.9497 (0.41); 1.8784 (0.41); 1.8542(0.49); 1.8243 (0.41); 1.8044 (0.39); 1.7436 (0.95); 1.6415 (4.55);1.6111 (5.01); 1.5785 (2.80); 1.4010 (1.04); 1.3847 (1.62); 1.3681(1.68); 1.3366 (1.23); 1.3084 (1.11); 1.2800 (1.03); 1.2341 (1.80);1.2104 (1.35); 1.1912 (1.65); 1.1614 (1.95); 1.1342 (2.21); 1.0819(0.56); 0.8920 (0.80); 0.8666 (1.26); 0.8415 (1.15); −0.0002 (0.94) 447.9522 (0.38); 7.0525 (2.11); 6.9179 (4.58); 6.7833 (2.36); 3.7615(16.00); 3.3491 (238.48); 3.2890 (1.80); 3.1048 (0.42); 2.8907 (3.00);2.7305 (2.49); 2.6766 (0.43); 2.6720 (0.57); 2.6675 (0.43); 2.5254(1.60); 2.5119 (29.42); 2.5075 (59.03); 2.5030 (78.06); 2.4985 (58.82);2.4941 (30.15); 2.3343 (0.39); 2.3298 (0.53); 2.3252 (0.39); 1.9148(0.61); 1.7731 (0.54); 1.7567 (1.34); 1.7400 (1.57); 1.7222 (1.37);1.7054 (1.07); 1.6882 (0.73); 1.6330 (4.86); 1.6101 (7.27); 1.3870(0.45); 1.2927 (1.56); 1.2804 (1.58); 1.2612 (1.42); 1.2346 (1.73);1.2143 (1.16); 1.1823 (1.61); 1.1522 (2.12); 1.1283 (2.60); 1.1079(1.28); 1.0770 (0.66); 0.8510 (1.58); 0.8260 (1.32); −0.0002 (1.37) 457.9987 (3.36); 7.9528 (0.46); 7.1170 (1.88); 6.9814 (4.11); 6.8458(2.07); 4.1043 (0.39); 3.9482 (1.03); 3.9084 (1.31); 3.8900 (16.00);3.3428 (160.48); 3.2825 (1.34); 3.2758 (1.34); 3.1904 (8.63); 2.8908(3.32); 2.7310 (2.77); 2.6764 (0.37); 2.6720 (0.48); 2.6673 (0.37);2.5251 (1.33); 2.5116 (26.46); 2.5073 (52.67); 2.5028 (69.73); 2.4984(53.14); 2.3341 (0.35); 2.3295 (0.47); 2.3251 (0.36); 1.7863 (0.52);1.7656 (0.71); 1.7508 (0.83); 1.7300 (0.67); 1.7104 (0.33); 1.5733(3.35); 1.5372 (1.54); 1.5180 (1.45); 1.5018 (1.35); 1.4817 (1.20);1.4648 (1.06); 1.4494 (0.74); 1.3872 (0.94); 1.3605 (0.83); 1.3515(0.89); 1.3395 (0.79); 1.3182 (1.04); 1.3077 (0.83); 1.2857 (0.77);1.2350 (0.67); −0.0002 (1.79) 46 7.9520 (0.50); 7.0881 (1.52); 6.9536(3.21); 6.8192 (1.64); 4.6861 (0.68); 3.9105 (0.47); 3.8613 (16.00);3.3465 (224.55); 3.2293 (1.73); 3.2141 (5.93); 3.1360 (1.45); 3.0671(0.72); 2.8907 (3.66); 2.7309 (3.23); 2.6721 (0.65); 2.5250 (1.73);2.5113 (32.90); 2.5073 (65.99); 2.5028 (87.90); 2.4984 (67.41); 2.3296(0.63); 1.7927 (0.64); 1.6100 (2.92); 1.5519 (2.83); 1.4869 (2.29);1.3869 (0.35); 1.2800 (1.31); 1.2469 (1.01); 1.2350 (1.34); 1.2104(0.39); −0.0002 (1.66) 47 7.9523 (0.39); 7.0488 (2.39); 6.9141 (5.08);6.7795 (2.62); 4.6477 (0.34); 3.7639 (16.00); 3.5127 (0.35); 3.3433(143.03); 3.1913 (4.68); 3.1008 (0.37); 2.8906 (3.07); 2.7304 (2.60);2.6762 (0.42); 2.6716 (0.53); 2.6672 (0.41); 2.5250 (1.48); 2.5115(26.82); 2.5071 (53.87); 2.5026 (71.30); 2.4980 (53.46); 2.4937 (27.21);2.3293 (0.45); 2.3249 (0.33); 1.7674 (0.68); 1.6207 (2.24); 1.5984(3.05); 1.5629 (2.17); 1.5304 (1.62); 1.5107 (1.45); 1.4954 (1.52);1.4756 (1.46); 1.4582 (1.31); 1.4429 (1.06); 1.4069 (0.84); 1.3872(0.85); 1.2889 (1.07); 1.2803 (1.14); 1.2581 (0.92); 1.2347 (1.07);−0.0002 (2.21) 48 7.9520 (0.55); 7.1071 (1.08); 6.9727 (2.16); 6.9471(0.57); 6.8380 (1.15); 6.8135 (0.33); 4.1100 (0.64); 4.0199 (0.75);3.7653 (16.00); 3.7027 (0.34); 3.5840 (0.33); 3.4124 (3.86); 3.3582(492.67); 3.2743 (0.57); 3.2538 (0.48); 3.2288 (0.39); 3.1681 (0.47);2.8912 (4.38); 2.7311 (3.51); 2.6772 (0.64); 2.6727 (0.86); 2.6683(0.65); 2.5623 (0.47); 2.5484 (0.91); 2.5344 (1.06); 2.5261 (2.67);2.5126 (46.77); 2.5082 (92.70); 2.5037 (121.86); 2.4991 (90.76); 2.4947(45.97); 2.3349 (0.62); 2.3304 (0.85); 2.3258 (0.62); 2.1811 (1.49);2.1373 (1.24); 2.0609 (2.00); 2.0386 (1.49); 2.0225 (1.36); 2.0072(1.22); 1.9913 (0.92); 1.9746 (0.47); 1.9101 (2.74); 1.8907 (1.99);1.8758 (1.92); 1.7478 (1.36); 1.7255 (1.67); 1.7202 (1.76); 1.7145(1.91); 1.6956 (1.22); 1.6850 (1.06); 1.6662 (0.80); 1.6411 (1.13);1.6062 (1.58); 1.5938 (1.42); 1.5703 (0.80); 1.5604 (0.57); 1.4357(3.76); 1.4275 (3.74); 1.4137 (2.93); 1.3927 (3.13); 1.3780 (2.69);1.3116 (0.99); 1.2805 (2.04); 1.2585 (1.90); 1.2347 (1.71); 1.2244(1.11); 1.2085 (1.11); 1.1620 (1.22); 1.1330 (2.26); 1.0921 (3.31);1.0553 (2.50); 1.0323 (1.71); 0.9964 (1.66); 0.9776 (1.70); 0.9122(0.39); 0.8887 (0.52); 0.8535 (0.55); −0.0002 (1.13) 49 8.3353 (0.43);8.2278 (5.39); 7.9524 (0.65); 7.8465 (0.36); 7.3558 (0.89); 7.2202(1.84); 7.2009 (0.59); 7.0841 (0.97); 4.1438 (0.55); 4.0694 (0.82);3.9707 (1.00); 3.9080 (2.81); 3.8956 (16.00); 3.5676 (1.30); 3.5517(0.83); 3.5118 (1.26); 3.4190 (0.64); 3.4099 (0.63); 3.4006 (0.60);3.3934 (0.61); 3.3464 (288.28); 3.2899 (0.44); 3.2794 (0.34); 2.8908(4.49); 2.7309 (3.74); 2.6718 (0.71); 2.6678 (0.57); 2.5604 (0.94);2.5466 (1.82); 2.5325 (1.36); 2.5253 (2.14); 2.5075 (80.99); 2.5030(107.35); 2.4986 (82.13); 2.3342 (0.54); 2.3298 (0.73); 2.1860 (1.26);2.1346 (1.10); 2.0910 (1.21); 2.0291 (0.42); 1.9636 (0.83); 1.9247(2.70); 1.9014 (2.68); 1.8925 (2.80); 1.8742 (1.09); 1.8536 (0.79);1.8359 (1.07); 1.8104 (1.22); 1.7969 (1.11); 1.7723 (0.80); 1.7396(0.89); 1.7180 (0.73); 1.6529 (1.26); 1.6148 (0.93); 1.5918 (0.88);1.5679 (0.54); 1.4350 (3.17); 1.3868 (2.53); 1.3639 (1.67); 1.3202(0.92); 1.2877 (2.32); 1.2655 (2.63); 1.2346 (1.59); 1.1708 (0.96);1.1320 (1.39); 1.0886 (2.81); 1.0538 (2.46); 0.9897 (1.24); −0.0002(2.49) 50 7.9519 (0.44); 7.1569 (0.37); 7.1348 (0.35); 7.0964 (1.05);7.0227 (0.78); 7.0005 (0.70); 6.9617 (2.11); 6.8884 (0.42); 6.8665(0.37); 6.8272 (1.13); 4.1172 (0.36); 4.0170 (0.43); 3.9106 (0.51);3.8604 (16.00); 3.6492 (0.33); 3.4681 (0.33); 3.4381 (1.21); 3.4282(1.19); 3.4187 (1.26); 3.3988 (0.52); 3.3429 (225.91); 3.2903 (1.05);3.2743 (1.05); 3.2629 (1.18); 3.2455 (0.73); 3.2116 (0.61); 3.1964(1.03); 3.1791 (0.81); 3.1570 (0.52); 3.1394 (0.47); 3.1218 (0.37);2.9649 (0.35); 2.8907 (3.32); 2.7310 (2.69); 2.6760 (0.53); 2.6717(0.74); 2.6671 (0.55); 2.5250 (2.02); 2.5115 (40.23); 2.5072 (80.67);2.5027 (106.81); 2.4982 (80.96); 2.3339 (0.56); 2.3293 (0.75); 2.3248(0.59); 2.1909 (1.15); 2.1475 (0.74); 2.0855 (0.90); 2.0476 (0.82);1.9982 (1.03); 1.9828 (0.93); 1.9681 (0.82); 1.9354 (1.52); 1.8991(1.76); 1.8863 (1.78); 1.8588 (1.28); 1.8423 (1.04); 1.7907 (0.40);1.7571 (0.87); 1.7221 (1.92); 1.6840 (1.00); 1.6664 (1.02); 1.6503(0.84); 1.6369 (0.70); 1.6214 (0.60); 1.5897 (0.53); 1.5678 (0.44);1.5580 (0.40); 1.5123 (0.73); 1.4487 (2.51); 1.4324 (2.58); 1.3870(1.35); 1.3497 (1.82); 1.3283 (1.34); 1.2946 (1.16); 1.2680 (1.25);1.2348 (2.13); 1.1655 (0.93); 1.1456 (1.77); 1.1276 (1.94); 1.0950(2.62); 1.0659 (2.18); 1.0475 (1.53); 1.0280 (1.16); 0.9970 (1.75);0.9776 (2.23); 0.9332 (0.44); 0.8999 (0.45); 0.8779 (0.40); 0.8488(1.15); −0.0002 (2.63) 51⁽*⁾  7.2841 (37.11); 7.0201 (0.47); 5.3224(16.00); 5.2528 (0.85); 5.2462 (1.41); 5.2331 (0.78); 5.2263 (1.00);4.4371 (0.48); 4.4195 (0.53); 4.4005 (0.56); 3.8542 (0.77); 3.8364(0.84); 3.8064 (15.60); 3.7771 (0.57); 3.7671 (0.57); 3.7559 (1.22);3.7482 (1.06); 3.7372 (1.07); 3.7273 (1.04); 3.7188 (0.85); 3.7002(0.33); 3.6193 (0.50); 3.5996 (0.91); 3.5906 (0.54); 3.5785 (0.58);3.5701 (0.62); 2.1935 (1.52); 2.1705 (0.35); 2.1588 (0.43); 2.1396(0.84); 2.1298 (1.44); 2.1132 (1.03); 2.1073 (1.79); 2.0967 (1.35);2.0865 (1.25); 2.0768 (1.29); 2.0731 (1.20); 2.0611 (1.12); 2.0501(0.79); 2.0284 (3.03); 2.0190 (4.16); 1.9778 (2.75); 1.9706 (3.27);1.9634 (3.03); 1.9433 (1.79); 1.9294 (1.96); 1.9211 (1.23); 1.9097(1.23); 1.8927 (0.56); 1.8867 (0.41); 1.8822 (0.37); 1.7834 (1.54);1.7522 (4.02); 1.7115 (7.44); 1.6795 (5.57); 1.5915 (2.50); 1.5630(11.25); 1.5268 (0.44); 1.5119 (1.51); 1.4821 (2.19); 1.3744 (2.28);1.3704 (2.28); 1.3448 (1.58); 1.2795 (0.38) 52⁽*⁾  7.2840 (24.75);7.0280 (1.36); 6.8913 (2.69); 6.8232 (0.40); 6.7546 (1.42); 5.3212(2.50); 4.9628 (0.32); 4.9551 (0.66); 4.9454 (0.58); 4.9365 (0.96);4.9287 (0.98); 4.9190 (0.59); 4.9101 (0.65); 4.9026 (0.34); 4.1390(0.77); 4.1229 (0.86); 4.1120 (0.78); 4.0191 (0.46); 3.9937 (0.67);3.9840 (1.07); 3.9653 (0.95); 3.9453 (0.72); 3.9247 (1.42); 3.9095(0.52); 3.9032 (0.94); 3.8887 (0.67); 3.8666 (0.43); 3.7915 (16.00);3.7890 (14.19); 3.7869 (13.96); 3.5930 (1.62); 3.5760 (3.59); 3.5587(1.75); 2.2372 (0.68); 2.2297 (0.70); 2.2132 (0.87); 2.2055 (1.45);2.1971 (0.89); 2.1918 (1.47); 2.1809 (1.05); 2.1723 (1.44); 2.1576(1.10); 2.1501 (0.95); 2.1389 (1.66); 2.1290 (2.05); 2.1173 (3.70);2.1020 (3.59); 2.0843 (1.35); 2.0703 (1.21); 2.0522 (1.22); 2.0348(0.46); 2.0273 (0.53); 1.9783 (0.45); 1.9738 (0.65); 1.9610 (1.19);1.9448 (1.93); 1.9295 (1.51); 1.9252 (1.58); 1.9171 (2.12); 1.9083(1.80); 1.8960 (1.73); 1.8876 (1.09); 1.8795 (1.85); 1.8699 (1.18);1.7771 (0.60); 1.7686 (0.67); 1.7536 (1.10); 1.7470 (1.35); 1.7080(0.96); 1.7012 (0.96); 1.6774 (1.44); 1.6540 (2.19); 1.6226 (1.92);1.6003 (0.92); 1.5909 (0.92); 1.5697 (7.55); 1.5471 (1.03); 1.4783(0.83); 1.4744 (0.85); 1.4710 (0.83); 1.4425 (1.00); 1.3880 (1.71);1.3785 (1.59); 1.3614 (1.80); 1.3537 (2.18); 1.3443 (1.50); 1.3274(1.17); 1.3174 (1.10); 1.3057 (0.57); 1.2978 (0.76); 1.2838 (0.42);1.2743 (0.82); 1.2663 (1.09); 1.2593 (1.62); 1.2509 (1.46); 1.2327(3.05); 1.2263 (4.08); 1.2159 (1.94); 1.2104 (1.69); 1.2019 (2.91);1.1940 (2.64); 1.1894 (1.92); 1.1826 (1.69); 1.1727 (1.20); 1.1670(1.81); 1.1563 (1.91); 1.1412 (1.33); 1.1322 (3.02); 1.1257 (2.32);1.1119 (2.58); 1.1037 (2.35); 1.0914 (1.68); 1.0833 (2.43); 1.0754(1.90); 1.0608 (1.33); 1.0540 (1.62); 1.0324 (0.67); 1.0238 (0.62);1.0150 (0.35); 0.9163 (0.39); 0.9081 (0.62); 0.8784 (1.07); 0.8556(0.72); 0.8488 (0.80); 0.8186 (0.34); 0.4745 (0.39); 0.4529 (0.68);0.4444 (0.80); 0.4225 (0.64); 0.4164 (0.71) Note ⁽*⁾ in CDCl₃

The following examples illustrate in a non-limiting manner thepreparation and efficacy of the compounds of formula (I) according tothe invention.

GENERAL PREPARATION EXAMPLE 1 Preparation of Amide of Formula (I) onChemspeed™ Apparatus

In a 13 mL Chemspeed™ vial is distributed 4 mL of a 0.15 M solution ofthe amine (11) (0.60 mmol) in dichloromethane followed by 0.72 mmol oftriethylamine. At a rate of 1 mL/min, 2 mL of a 0.30 M solution of theacyl chloride (111) (0.60 mmol) are added and the mixture is thenstirred at room temperature overnight. 1 mL of water is then added andthe mixture is poured over a basic alumina cartridge (2 g) and elutedwith dichloromethane. The solvents are removed and the crude amidederivative is analyzed by HPLC-MS and NMR. Insufficiently pure compoundsare further purified by preparative LC.

GENERAL PREPARATION EXAMPLE 2 Thionation of Amide of Formula (I) onChemspeed™ Apparatus

In a 13 mL Chemspeed™ vial is weighted 0.27 mmol of phosphorouspentasulfide (P₂S₅). 3 mL of a 0.18 M solution of the amide (1) (0.54mmol) in dioxane is added and the mixture is heated at reflux for twohours. The temperature is then cooled to 80° C. and 2.5 mL of water areadded. The mixture is heated at 80° C. for one more hour. 2 mL of waterare then added and the reaction mixture is extracted twice by 4 mL ofdichloromethane. The organic phase is deposited on a basic aluminacartridge (2 g) and eluted twice by 8 mL of dichloromethane. Thesolvents are removed and the crude thioamide derivative is analyzed byHPLC-MS and NMR. Insufficiently pure compounds are further purified bypreparative LC.

EXAMPLE A In Vivo Preventive Test on Sphaerotheca Fulicinea (Cucumber)

Solvent: 49 parts by weight of N,N-dimethylformamideEmulsifier: 1 part by weight of alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Sphaerotheca fuliginea. Then the plants are placedin a greenhouse at approximately 23° C. and a relative atmospherichumidity of approximately 70%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table A:

TABLE A Example Efficacy 8 98 9 95 10 90 11 95 14 70 15 85 17 100 24 9525 100 26 100 48 100 49 90

EXAMPLE B In Vivo Preventive Test on Alternaria solani (Tomato)

Solvent: 49 parts by weight of N,N-dimethylformamideEmulsifier: 1 part by weight of alkylarylpolyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Alternaria solani. The plants remain for one day inan incubation cabinet at approximately 22° C. and a relative atmospherichumidity of 100%. Then the plants are placed in an incubation cabinet atapproximately 20° C. and a relative atmospheric humidity of 96%.

The test is evaluated 7 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table B:

TABLE B Example Efficacy 6 94 7 94 9 89 10 94 11 94 12 94 13 94 14 94 1589 16 94 17 94 20 100 21 100 22 100 23 88 24 94 25 90 26 100 29 94 30 8931 89 32 94 35 94 36 88 37 94 40 94 42 78 44 89 47 89 48 100 49 94 50 88

Under the same conditions, high (at least 85%) to total protection isobserved at a dose of 500 and 100 ppm of active ingredient with compoundof example 12, 20 and 25, whereas poor (less than 20%) protection to100% of plant damages is observed with compound 1.006, compound CMP1(chloro analogue of compound 1.006) and compound CMP2 (fluoro analogueof compound 1.006) claimed in patent application WO-2009/153191 as intable B2:

TABLE B2 Example dose (ppm) Efficacy 12 from this patent 500 94 100 8920 from this patent 500 100  100 94 25 from this patent 500 90 100 901.006 from WO-2009/153191 500 —^((a)) 100   20 ^((b)) CMP1 fromWO-2009/153191 500 —^((a)) 100 —^((a)) CMP2 from WO-2009/153191 500—^((a)) 100 —^((a)) note ^((a))together with 100% of plant damages note^((b)) together with 50% of plant damages

Compound 1.006 claimed in international patent WO-2009/153191corresponds to[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]{(2S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone,

compound CMP1 claimed in international patent WO-2009/153191 correspondsto[5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]{(2S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone,andcompound CMP2 claimed in international patent WO-2009/153191 correspondsto[3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazol-4-yl]{(2S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone.

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2009/153191.

EXAMPLE C In Vivo Preventive Test on Pyrenophora teres (Barley)

Solvent: 49 parts by weight of N,N-dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound at the stated rate of application. Oneday after this treatment, the plants are inoculated with an aqueousspore suspension of Pyrenophora teres.

The plants remain for 48 hours in an incubation cabinet at 22° C. and arelative atmospheric humidity of 100%. Then the plants are placed in agreenhouse at a temperature of approximately 20° C. and a relativeatmospheric humidity of approximately 80%.

The test is evaluated 7-9 days after the inoculation. 0% means anefficacy which corresponds to that of the untreated control while anefficacy of 100% means that no disease is observed.

Under these conditions, good (at least 70%) to total protection isobserved at a dose of 500 ppm of active ingredient with the followingcompounds from table C:

TABLE C Example Efficacy 1 100 2 100 6 95 7 100 8 100 9 100 10 100 11100 12 100 13 100 14 100 15 100 16 100 17 100 18 89 19 94 20 100 21 10022 100 23 100 24 100 25 100 26 100 29 100 30 95 31 90 32 100 33 94 34 9435 94 36 78 37 94 38 89 40 95 41 70 42 95 43 90 44 100 47 100 48 100 49100 50 100

EXAMPLE D In Vivo Preventive Test on Leptosphaeria nodorum (Wheat)

Solvent: 49 parts by weight of N,N-dimethylacetamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier, and the concentrate is dilutedwith water to the desired concentration.

To test for preventive activity, young plants are sprayed with thepreparation of active compound or active compound combination at thestated rate of application. After the spray coating has been dried, theplants are sprayed with a spore suspension of Leptosphaeria nodorum.

The plants remain for 48 hours in an incubation cabinet at approximately20° C. and a relative atmospheric humidity of approximately 100%.

The plants are placed in the greenhouse at a temperature ofapproximately 22° C. and a relative atmospheric humidity ofapproximately 80%.

The test is evaluated 8 days after the inoculation. 0% means an efficacywhich corresponds to that of the untreated control, while an efficacy of100% means that no disease is observed.

Under these conditions, good (at least 70%) to excellent (at least 95%)protection is observed at a dose of 500 ppm of active ingredient withthe following compounds from table D:

TABLE D Example Efficacy 8 95 11 95 16 70 17 95 48 90 49 70

Under the same conditions, high (at least 80%) to excellent (at least95%) protection is observed at a dose of 500 and 100 ppm of activeingredient with compound of example 8, 11 and 17, whereas average (lessthan 60%) to no protection is observed with compound 1.006 or compoundCMP1 (chloro analogue of compound 1.006) claimed in patent applicationWO-2009/153191 as in table D2:

TABLE D2 Example dose (ppm) Efficacy 8 from this patent 500 95 100 90 11from this patent 500 95 100 80 17 from this patent 500 95 100 80 1.006from WO-2009/153191 500 60 100 40 CMP1 from WO-2009/153191 500 0 100 0

Compound 1.006 claimed in international patent WO-2009/153191corresponds to[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]{(2S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone,and

compound CMP1 claimed in international patent WO-2009/153191 correspondsto[5-chloro-3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]{(2S)-2-[(2,4,6-trichlorophenoxy)methyl]pyrrolidin-1-yl}methanone,

These results show that the compounds according to the invention have amuch better biological activity than the structurally closest compoundsdisclosed in WO-2009/153191.

1. A compound of formula (I)

wherein T represents O or S; n represents 0, 1, 2 or 3; p represents 1or 2; Q¹ represents a direct bond; O; S; SO; or SO₂; provided that whenn represents 0 then Q¹ represents a direct bond; Z¹ and Z² independentlyrepresent a hydrogen atom; a halogen atom; cyano; substituted ornon-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 5 halogenatoms; substituted or non-substituted C₁-C₈-alkoxy; substituted ornon-substituted C₁-C₈-alkylsulfanyl; or substituted or non-substitutedC₁-C₈-alkoxycarbonyl; or two substituents Z¹ and Z², together with thecarbon atom to which they are linked can form a 3-, 4-, 5- or 6-memberedsaturated carbocycle that can be substituted by up to four C₁-C₈-alkylgroups; Z³ represents a hydrogen atom; or substituted or non-substitutedC₁-C₈-alkyl; B represents a substituted or non-substituted C₁-C₈-alkyl;C₁-C₈-halogenoalkyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxy-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylsulfanyl-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylsulfinyl-C₁-C₈-alkyl; substituted or non-substitutedC₁-C₈-alkylsulfonyl-C₁-C₈-alkyl; substituted or non-substitutedC₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9 halogen atoms;substituted or non-substituted (C₃-C₇-cycloalkyl)-C₁-C₈-alkyl;substituted or non-substituted C₄-C₇-cycloalkenyl;C₄-C₇-halogenocycloalkenyl having 1 to 9 halogen atoms; substituted ornon-substituted (C₄-C₇-cycloalkenyl)-C₁-C₈-alkyl; substituted ornon-substituted bicyclo[2.2.1]heptanyl; substituted or non-substitutedbicyclo[2.2.1]hept-2-enyl; substituted or non-substitutedbicyclo[2.2.2]octanyl; substituted or non-substitutedbicyclo[2.2.2]oct-2-enyl; substituted or non-substituted adamantyl;provided that when n represents 0 and Q¹ represents a direct bond then Bis not methyl or ethyl; R¹ and R³ independently represent a halogenatom; nitro; cyano; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; substitutedor non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;C₂-C₈-halogenoalkenyl having 1 to 9 halogen atoms; substituted ornon-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 9halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfonyl;C₁-C₈-halogenoalkylsulfonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylamino; substituted or non-substituteddi-C₁-C₈-alkylamino; substituted or non-substituted C₂-C₈-alkenyloxy;substituted or non-substituted C₃-C₈-alkynyloxy; substituted ornon-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9halogen atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;substituted or non-substituted C₁-C₈-alkylcarbonyl;C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonylhaving 1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; phenoxy; phenylsulfanyl phenylamino; benzyloxy;benzylsulfanyl; or benzylamino; R² represents a hydrogen atom; halogenatom; nitro; cyano; hydroxy; amino; sulfanyl; pentafluoro-λ⁶-sulfanyl;substituted or non-substituted (C₁-C₈-alkoxyimino)-C₁-C₈-alkyl;substituted or non-substituted (benzyloxyimino)-C₁-C₈-alkyl; substitutedor non-substituted C₁-C₈-alkyl; C₁-C₈-halogenoalkyl having 1 to 9halogen atoms; substituted or non-substituted C₂-C₈-alkenyl;C₂-C₈-halogenoalkenyl having 1 to 9 halogen atoms; substituted ornon-substituted C₂-C₈-alkynyl; C₂-C₈-halogenoalkynyl having 1 to 9halogen atoms; substituted or non-substituted C₁-C₈-alkoxy;C₁-C₈-halogenoalkoxy having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylsulfanyl; C₁-C₈-halogenoalkylsulfanyl having1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylsulfinyl; C₁-C₈-halogenoalkylsulfinyl having 1 to 9 halogenatoms; substituted or non-substituted C₁-C₈-alkylsulfonyl;C₁-C₈-halogenoalkylsulfonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkylamino; substituted or non-substituteddi-C₁-C₈-alkylamino; substituted or non-substituted C₂-C₈-alkenyloxy;substituted or non-substituted C₃-C₈-alkynyloxy; substituted ornon-substituted C₃-C₇-cycloalkyl; C₃-C₇-halogenocycloalkyl having 1 to 9halogen atoms; substituted or non-substituted tri(C₁-C₈)alkylsilyl;substituted or non-substituted C₁-C₈-alkylcarbonyl;C₁-C₈-halogenoalkylcarbonyl having 1 to 9 halogen atoms; substituted ornon-substituted C₁-C₈-alkoxycarbonyl; C₁-C₈-halogenoalkoxycarbonylhaving 1 to 9 halogen atoms; substituted or non-substitutedC₁-C₈-alkylcarbamoyl; substituted or non-substituteddi-C₁-C₈-alkylcarbamoyl; phenoxy; phenylsulfanyl; phenylamino;benzyloxy; benzylsulfanyl; or benzylamino; as well as its salts,N-oxides, metal complexes, metalloid complexes and optically activeisomers, provided that the following compounds are excluded:[2-(chloromethyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone[2-(chloromethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone[2-(3-chloropropyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone(3-tert-butyl-1-methyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone(3-tert-butyl-1-isopropyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone(1,3-dimethyl-1H-pyrazol-4-yl)[2-(2-hydroxyethyl)piperidin-1-yl]methanone[2-(2-hydroxyethyl)piperidin-1-yl](1-isopropyl-3-methyl-1H-pyrazol-4-yl)methanone{1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]pyrrolidin-2-yl}aceticacid[2-(hydroxymethyl)pyrrolidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone{2-[(methylamino)methyl]piperidin-1-yl}(1,3,5-trimethyl-1H-pyrazol-4-yl)methanone[2-(2-chloroethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone[(2S)-2-(chloromethyl)pyrrolidin-1-yl][3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl]methanone[3-(difluoromethyl)-1-methyl-1H-pyrazol-4-yl][(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]methanone[2-(methoxymethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone[2-(2-hydroxyethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone{1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]piperidin-2-yl}acetic acidmethyl{1-[(1,3,5-trimethyl-1H-pyrazol-4-yl)carbonyl]piperidin-2-yl}acetate[2-(hydroxymethyl)piperidin-1-yl](1,3,5-trimethyl-1H-pyrazol-4-yl)methanone.2. A compound according to claim 1 wherein R¹ represents a substitutedor non-substituted C₁-C₅-alkyl, C₁-C₅-halogenoalkyl comprising up to 9halogen atoms that can be the same or different, substituted ornon-substituted C₁-C₅-alkoxy; R² represents a hydrogen atom, or ahalogen atom; and R³ represents a substituted or non-substitutedC₁-C₅-alkyl.
 3. A compound according to claim 2 wherein R¹ representsdifluoromethyl; R² represents a chlorine atom, or a fluorine atom; andR³ represents a methyl.
 4. A compound according to claim 1 wherein Trepresents O.
 5. A compound according to claim 1 wherein p represents 1.6. A compound according to claim 1 wherein p represents
 2. 7. A compoundaccording to claim 1 wherein n represents 0 or
 1. 8. A compoundaccording to claim 1 wherein Q¹ represents a direct bond or an oxygenatom.
 9. A compound according to claim 8 wherein Q¹ represents a directbond.
 10. A compound according to claim 1 wherein B represents asubstituted or non-substituted C₁-C₈-alkyl, substituted ornon-substituted C₃-C₇-cycloalkyl, substituted or non-substitutedbicyclo[2.2.1]hept-2-yl, substituted or non-substitutedbicyclo[2.2.2]oct-2-yl or substituted or non-substituted adamantan-1-yl.11. A compound according to claim 1 wherein Z¹ and Z² independentlyrepresents a hydrogen atom, a halogen, substituted or non-substitutedC₁-C₈-alkyl or substituted or non-substituted C₁-C₈-alkoxy.
 12. Acompound according to claim 1 wherein Z³ represents a hydrogen atom. 13.A fungicide composition comprising, as an active ingredient, aneffective amount of a compound of formula (I) according to claim 1 andan agriculturally acceptable support, carrier or filler.
 14. A methodfor controlling phytopathogenic fungi of crops, characterized in that anagronomically effective and substantially non-phytotoxic quantity of acompound according to claim 1 is applied to the soil where plants growor are capable of growing, to the leaves and/or the fruit of plants orto the seeds of plants.
 15. Use of compounds of the formula (I)according to claim 1 for the control of phytopathogenic harmful fungi.16. Process for producing compositions for controlling phytopathogenicharmful fungi, characterized in that derivatives of the formula (I)according to claim 1 are mixed with extenders and/or surfactants. 17.Use of compounds of the formula (I) according to claim 1 for treatmentof plants, seeds, transgenic plants or transgenic seeds.
 18. A methodfor controlling phytopathogenic fungi of crops, characterized in that anagronomically effective and substantially non-phytotoxic quantity of acomposition according to claim 13 is applied to the soil where plantsgrow or are capable of growing, to the leaves and/or the fruit of plantsor to the seeds of plants.